Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines

Article abstract of DOI:10.1021/acs.joc.8b00649

The catalytic system generated in situ from the tetranuclear Ru-H complex with a catechol ligand (1/L1) was found to be effective for the direct deaminative coupling of two primary amines to form secondary amines. The catalyst 1/L1 was highly chemoselective for promoting the coupling of two different primary amines to afford unsymmetric secondary amines. The analogous coupling of aniline with primary amines formed aryl-substituted secondary amines. The treatment of aniline-d₇ with 4-methoxybenzylamine led to the coupling product with significant deuterium incorporation on CH₂ (18% D). The most pronounced carbon isotope effect was observed on the α-carbon of the product isolated from the coupling reaction of 4-methoxybenzylamine (C(1) = 1.015(2)). A Hammett plot was constructed from measuring the rates of the coupling reaction of 4-methoxyaniline with a series of para-substituted benzylamines 4-X-C₆H₄CH₂NH₂ (X = OMe, Me, H, F, CF₃) (ρ = -0.79 ± 0.1). A plausible mechanistic scheme has been proposed for the coupling reaction on the basis of these results. The catalytic coupling method provides an operationally simple and chemoselective synthesis of secondary amine products without using any reactive reagents or forming wasteful byproducts.

Full text of DOI:10.1021/acs.joc.8b00649

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Synthesis of Symmetric and Unsymmetric Secondary
Amines from the Ligand Promoted Ruthenium Catalyzed
Deaminative Coupling Reaction of Primary Amines
Pandula T. Kirinde Arachchige, Hanbin Lee, and Chae S. Yi
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00649 • Publication Date (Web): 18 Apr 2018
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Page 1 of 18
The Journal of Organic Chemistry
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Synthesis of Symmetric and Unsymmetric Secondary Amines from the
Ligand Promoted Ruthenium Catalyzed Deaminative Coupling Reaction of
Primary Amines
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Pandula T. Kirinde Arachchige, Hanbin Lee and Chae S. Yi*
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881 United States
KEYWORDS: secondary amine, deamination, ruthenium catalyst
[Ru-H]4 (0.75 mol %)
L1 (10 mol %)
C6H5Cl, 130 oC
+
+
NH3
R NH2
(1.0 mmol)
R’ NH2
(1.4 mmol)
R
N
H
R’
CO
H
Ru PCy3
CO
Cy3P
H
OH
OH
Ru
O
OH
t-Bu
OC Ru
H
Ru
H
L1
O
H
PCy
CO
3
PCy3
[Ru-H]4
ABSTRACT: The catalytic system generated in-situ from the tetranuclear Ru–H complex with a catechol ligand (
found to be effective for the direct deaminative coupling of two primary amines to form secondary amines. The catalyst
L1 was highly chemoselective for promoting the coupling of two different primary amines to afford unsymmetric second-
/
1 L1) was
1
/
ary amines. The analogous coupling of aniline with primary amines formed aryl-substituted secondary amines. The treat-
ment of aniline-d7 with 4-methoxybenzylamine led to the coupling product with significant deuterium incorporation on CH2
(18% D). The most pronounced carbon isotope effect was observed on the a-carbon of the product isolated from the cou-
pling reaction of 4-methoxybenzylamine (C(1) = 1.015(2)). Hammett plot was constructed from measuring the rates of the
coupling reaction of 4-methoxyaniline with a series of para-substituted benzylamines 4-X-C6H4CH2NH2 (X = OMe, Me, H, F,
CF3). (r = -0.79 ± 0.1). A plausible mechanistic scheme has been proposed for the coupling reaction on the basis of these
results. The catalytic coupling method provides an operationally simple and chemoselective synthesis of secondary amine
products without using any reactive reagents or forming wasteful byproducts.
Introduction
tion of arylamines with organoboranes, by exploiting a
directing group assisted sp2 C–N bond activation strategy.4
A few remarkably efficient amide-to-ester conversion
methods via amide C–N bond cleavage have been achieved
by using Ni catalysts.5 A number of Pd-catalyzed C–N
cleavage methods have also been developed, including
intramolecular Heck-type coupling reactions6 and allyla-
mine coupling reactions.7 Selective catalytic C–C coupling
methods via sp3 C–N bond activation of allyl- and benzylic
amines have been achieved.8 Other notable examples of
catalytic C–N bond cleavage reactions include: oxidative C–
H coupling reaction of amides with alkynes,9 and Milstein
group’s report on the Ru-catalyzed hydrogenolysis of am-
ides.10 Catalytic C–N cleavage methods have also been suc-
cessfully utilized for constructing nitrogen heterocycles.11
Designing catalytic C–N bond cleavage methods has at-
tracted considerable research efforts in the field of homo-
geneous catalysis since such methods are of fundamental
importance in a variety of industrial chemical syntheses as
well as in biochemical processes of nitrogen compounds.1
Even though catalytic C–N bond cleavage methods have
been recognized as an essential protocol for harnessing
nitrogen compounds from both petroleum and biomass
feedstocks, these catalytic methods have long been ham-
pered by a relatively strong C–N bond strength and cata-
lyst poisoning by the nitrogen substrates.2 In a pioneering
report, Fujiwara and co-workers first demonstrated the
direct coupling of olefins with arylamines, in which arene
sp2 C−N bond cleavage was promoted by a stoichiometric
amount of Pd(II) salts.3 More recently, Kakiuchi and co-
workers devised a ruthenium-catalyzed C–C coupling reac-
Chemoselective synthesis of amines has long been a per-
tinent issue in organic synthesis. Much research efforts has
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Page 2 of 18
been devoted to the development of new catalytic synthe- catechol ligand exhibited the most promising activity for
1
2
3
4
5
6
7
8
sis of amines, and transition metal catalyzed dehydrogena-
tive coupling strategies have emerged as highly effective
ways to activate amines and alcohols.12 In particular, late
transition metal catalysts have been successfully employed
to promote amine-to-alcohol coupling reactions via hydro-
gen borrowing strategy to synthesize unsymmetric sec-
ondary amines.13 Traditionally, the reductive amination
methods have also been commonly used for the synthesis
of secondary amines.14 Since these methods often require
stoichiometric reducing agents and/or additives, which
result in the formation of copious amounts of salt byprod-
ucts, catalytic deaminative coupling methods have been
recognized as an alternative strategy for the synthesis of
secondary amines. Beller and co-workers reported a highly
selective dealkylation of amines by using Shvo catalyst.15
Zhang group also devised the synthesis of unsymmetric
secondary amines from the coupling of aniline with prima-
ry amines by using soluble Co catalysts.16 From both eco-
nomic and environmental perspectives, the development
of chemoselective catalytic coupling methods via C–N bond
cleavage of amines and related nitrogen compounds still
remains an essential goal in the fields of homogeneous
catalysis and organic synthesis.
the coupling reaction, as analyzed by both GC and NMR
spectroscopic methods (Table 1). Among the screened
oxygen and nitrogen ligands, 4-(1,1-dimethylethyl)-1,2-
benzenediol (L1) was found to give the highest activity and
selectivity for these Ru catalysts in giving the unsymmetric
amine product 3a over the symmetric one 4a (entries 9
and 13). After further ligand screening and optimization
studies, we have chosen the standard condition for the 1.0
mmol scale coupling reaction as:
1
(0.75 mol %, 3 Ru mol
9
%)/L1 (10 mol %) in chlorobenzene (2 mL) at 130 °C (Ta-
bles S1 and S2, Supporting Information (SI)). A 3:1 ratio of
catechol ligand to Ru catalyst was found to be the optimum
for the catalytic activity, as a lower ratio (2:1) typically
gave a lower product yield. Non-protic polar solvents such
as chlorobenzene and dioxane afforded the highest prod-
uct yields and selectivity, and the for the sake of consisten-
cy, we have chosen chlorobenzene as the solvent for all
coupling reactions. The formation of the byproduct ammo-
nia was detected in the crude mixture as analyzed by both
NMR and GC-MS methods.
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Table 1. Catalyst and Ligand Screening Studya
b
en-
catalyst
ligand
yield
3a 4a
( : )
c
try
We previously disclosed the synthesis of unsymmetrical
ethers from the dehydrative coupling reactions of alcohols
and aldehydes that are catalyzed by a well-defined cationic
ruthenium-hydride complex.17 Since these coupling reac-
tions are driven by the formation of water, we reasoned
that the analogous deaminative coupling reactions of
amines could be achieved, where the formation of ammo-
nia would serve as the driving force for such coupling reac-
tions. Herein, we report the synthesis of symmetric and
unsymmetric secondary amines from the catalytic deami-
native coupling of primary amines. The catalytic method
exhibits high chemoselectivity as well as a broad substrate
scope in forming secondary amines, while generating am-
monia as the only byproduct.
1
2
3
4
5
6
7
1
1
1
1
1
1
1
none
27:7
phenol
52:16
68:20
19:6
1,2-catechol
aniline
2-NH2PhCOMe
PhCONH2
1,1’-BINOL
28:16
trace
trace
8
9
1
1
1,2-C6H4(NH2)2
L1
27:12
74:22
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12
13
14
15
16
17
18
19
20
1
1
L2
L3
L1
L1
L1
L1
L1
L1
L1
L1
L1
67:6
62:13
65:1
70:16
60:5
14:7
0
1
2
2
/HBF4·OEt2
/HBF4·OEt2
Results and Discussion
We previously devised a catalytic system comprised of
the cationic Ru–H complex and a phenol ligand, which was
found to exhibit high catalytic activity for the hydrogenoly-
sis of carbonyl compounds to yield the corresponding ali-
phatic products.18 By adopting the similar ligand con-
trolled catalysis strategy, we initially screened soluble Ru
catalysts with phenol and related oxygen and nitrogen
ligands to promote the C–N bond activation reactions. We
have chosen the coupling reaction of benzylamine with
cyclohexylamine as a test case to screen both Ru catalysts
and the ligands (eq 1).
[Ru(COD)Cl2]x
RuCl3·3H2O
(PPh3)3(CO)RuH2
[(p-cymene)RuCl2]2
RuHCl(CO)(PCy3)2
[(PCy3)2(CO)(CH3CN)2RuH]
0
<1
70:15
0
BF4
a Reaction conditions: benzylamine (0.5 mmol), cyclohexylamine (0.7
mmol), catalyst (3 mol %), ligand (10 mol %), chlorobenzene (2 mL),
130 °C, 16 h. b See the Supporting Information for extensive list and
structure of ligands. c The product yield was determined by 1H NMR
using C6Me6 as the internal standard.
[Ru] (3 mol %)
L (10 mol %)
NH2
NH3
+
Ph
+
Ph
N
H
Ph
N
H
Ph
(1)
C6H5Cl, 130 o
C
-NH3
3a
4a
(1.0 mmol) (1.0 mmol)
We explored the substrate scope of the deaminative
coupling reaction by using the optimized catalyst system
1 L1 under the standard condition (Table 2). The coupling
/
of benzylic amines with a variety of aliphatic and benzylic
primary amines selectively formed the unsymmetric sec-
ondary amine products 3a-
3m. An excess amount (1.4
H
CO
Ru
CO
Cy3P
H
Ru PCy3
BF4
Ru
O
OH
H
PCy3
OC Ru
H
Ru
H
OC
O
H
PCy3
2
CO
PCy3
1
equiv) of the second amine (usually more electron rich
amine) was found to improve the product selectivity for
Among the initially screened Ru catalysts, both the
tetranuclear Ru-H complex [(PCy3)(CO)RuH]4(O)(OH)2 (
1
)
-
and the cationic [(C6H6)(PCy3)(CO)RuH]+BF4
(
2
) with 1,2-
unsymmetric amines
3
. Typically, <20 % of the symmetric
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The Journal of Organic Chemistry
amine products was formed in the crude mixture in most
product 4l was obtained in case of (R)-4-methoxy-a-
1
2
3
4
5
6
7
8
cases, and analytically pure unsymmetric amine products
were readily isolated after silica gel column chromato-
graphic separation. The major byproducts, symmetric
methylbenzenemethaneamine (d.r. = 7:1). The catalytic
method delivers a operationally simple synthesis of sym-
metric secondary amines from readily available primary
amines without using any reactive reagents via a deamina-
tive coupling method.14,16
amine products
4
were detected by TLC and GC/MS, but
were not isolated in these cases. The coupling of phenethyl
amines with both benzylic and aliphatic amines also gave
the selective formation of 3n-
3v. Indole-, Furanyl- and
phenol-substituted amines with cyclohexylamine selective-
ly yielded the unsymmetric secondary amine products
Table 3. Synthesis of Symmetric Secondary Aminesa
X
X
O
O
O
O
N
N
H
N
H
H
X
X
4j (77%)
9
(84%)
(89%)
4a
4b
4h
4i
(89%)
(94%)
X = OMe
X = Cl
X = H
X = Me
-
3bb 3dd. For these cases, the coupling of benzylic and oth-
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4c X = OMe (86%)
er aryl-substituted amines with electron-rich amines tend
to favor the formation of unsymmetrical amines over the
symmetrical ones. In contrast, the coupling of two different
aliphatic amines with sterically non-demanding group
yielded in a mixture of symmetric and unsymmetric
amines. The coupling reaction with secondary and tertiary
amines was found to be very sluggish and unselective, re-
sulting in a complex mixture of products. The catalytic
coupling method is operationally simple and exhibits high
chemoselectivity toward the formation of unsymmetric
secondary amines without resorting to employing any re-
active reagents.
MeO
MeO
OMe
OMe
X = Cl
X = Ph
X = F
4d
4e
4f
(92%)
(85%)
(91%)
N
H
N
H
MeO
OMe
4g X = CF3 (84%)
4l d.r. = 7:1 (75%)
OMe
OMe
4k (61%)
H
N
H
N
NH
Ph
Ph
4p d.r. = 1:1 (93%)
R1
R1
R2
R2
H
4r (73%)
Ph
N
Ph
(89%)
(90%)
(87%)
4m
4n
R1 = OMe, R2 = H
R1 = H, R2 = OMe
4o R1 = H, R2 = F
R
N
H
R
4q d.r. = 1:1 (90%)
S
H
N
S
b
b
(43%)
(46%)
(79%)
(42%)
R = n-pentyl
4u
4v R = n-propyl
4w
N
H
R = 2-furyl
4x R = CH CH Ph
b
4t (89%)
4s (95%)
2
2
a
Reaction conditions: amine (1.0 mmol),
1
(0.75 mol %), L1 (10 mol
b
%), chlorobenzene (2 mL), 130 °C, 16 h. 40-50% of tertiary amines
formed.
Table 2. Synthesis of Unsymmetric Secondary Amines from
the Deaminative Coupling of Primary Aminesa
To further illustrate the synthetic versatility of catalytic
coupling method, we next explored the coupling reaction
of aniline derivatives with primary amine substrates of
biological relevance (Table 4). The coupling of para-
substituted anilines with benzylic amines led to the selec-
1 (0.75 mol %)
L1 (10 mol %)
C6H5Cl (2 mL), 130 o
t-Bu
OH
OH
R
R'
R
R
+
+
N
H
4
+
NH3
R
NH2
R' NH2
N
H
3
C
(1.0 mmol)
(1.4 mmol)
L1
tive formation of unsymmetric amine products 5a-
5e
without any significant amount of the symmetric amine
products. Similarly, the reaction of para-substituted ani-
lines with 3,4,5-trimethoxybenzylamine afforded the cou-
pling products 5f-
5h in high yields. Single crystals of 5f
were obtained by slow evaporation in CH2Cl2/hexanes, and
R
R
N
H
N
H
N
H
X
X
F
3e
3f
3g
(73%)
(78%)
(71%)
(59%)
(57%)
(66%)
(56%)
(55%)
(72%)
3j R = n-hexyl
3k
3a
3b
3c
3d
X = Cl R = CH2CH2Ar
X = Ph R = n-hexyl
(63%)
(66%)
(55%)
(58%)
X = H
X = OMe
X = F
R = CH2Ar
3l R = CH2CH2Ar
X = Ph
R = CH2Ar’
X = CF3
R = CH2CH(CH3)Ph
3h X = CF3 R = n-hexyl
3i
3m
R = CH CH CO Et
X = H
2
2
2
its structure was determined by X-ray crystallography.
H
N
H
N
F
R
N
H
O
R
R
The treatment of 3-amino-9-ethylcarbazole with n-
hexylamine predictively yielded the product 5q. The cou-
O
MeO
(59%)
(60%)
(56%)
(76%)
(58%)
R = cyclohexyl
R = CHMeAr
R = CH2CHMePh
3u R = 2-Indanyl
3w
3x
3y
(70%)
(51%)
(80%)
(54%)
(65%)
(73%)
(55%)
3n
3o
3p
3q
3r
R = Bn
R = n-hexyl
R = cyclohexyl
R = 2-Indanyl
R = CHMeAr
3v
R = CHMeAr
pling
of
(R)-(+)-aminoglutathimide
with
3,4,5-
trimethoxybenzylamine led to the optically active coupling
product (R)-5r, without any detectable racemization. The
coupling of L-glutamine with 3-phenylpropylamine and 4-
methoxybenzylamine led to the cyclized amine products 5s
and 5t in 75% and 70% yields, respectively. The formation
of cyclized products 5s and 5t can be rationalized by initial
dehydrative cyclization of glutamine followed by the de-
aminative coupling with the primary amine substrates. The
optimized standard conditions were used for all of these
coupling reactions as described in Tables 2-4, with slight
modifications on the reaction time and temperature.
3s R = CHMeCH2CH2Ph
3t
R = CH2Ar
H
N
H
N
HN
R
MeO
O
Cy
H
N
Cy
N
H
Cy
HO
(46%)
(63%)
R = n-hexyl
3z
3aa R = CH2CH2Ar
3dd (69%)
3cc (69%)
3bb (80%)
a Reaction conditions: R-NH2 (1.0 mmol), R’-NH2 (1.4 mmol),
1
(0.75
mol %), L1 (10 mol %), chlorobenzene (2 mL), 130 °C, 16 h. Ar =
C6H4-4-OMe.
We next explored the substrate scope for the formation
of symmetric secondary amines by using the catalyst sys-
tem
1
/
L1 (Table 3). Benzylic primary amines reacted
We monitored the amine coupling reaction by NMR
spectroscopy to probe the overall reaction profile. In a J-
Young NMR tube equipped with Teflon stopcock, 4-
methoxybenzylamine (34 mg, 0.25 mmol) and the catalyst
smoothly to afford the secondary amine products 4a
-
4k
without the formation of tertiary amines or other side
products. The coupling of both phenethyl and indanyl
amines formed the corresponding secondary amine prod-
system
1
(3 mg, 0.75 mol %)/L1 (4 mg, 10 mol %) were
ucts 4m-
4r. While cyclohexyl and thiophene-substituted
dissolved in toluene-d8 (0.5 mL). The tube was immersed
in an oil bath at 130 °C, and the reaction progress was
monitored by 1H NMR in 20 min intervals.
amines predictively yielded the corresponding secondary
amine products 4s and 4t, respectively, a mixture of sec-
ondary and tertiary amines was formed for sterically non-
demanding aliphatic amines 4u
of chiral primary amines led to a 1:1 diastereomeric mix-
ture of products as illustrated by the formation of 4p
4q
but interestingly, a diastereoselective formation of the
-
4x. Generally, the coupling
Table 4. Synthesis of Unsymmetric Secondary Amines from
the Deaminative Coupling of Anilines with Aminesa
-
,
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H
matography, and its deuterium content was analyzed by 1H
and 2H NMR (Figure S1, SI). A significant amount of deuter-
ium was incorporated to the CH2 position of 5a-d (18% D),
without any deuterium exchange on the arene C–H posi-
tions. In a control experiment, the treatment of the isolated
1 (0.75 mol %)
L1 (10 mol %)
C6H5Cl (2 mL), 130 o
N
R
+
NH2
R
+
NH3
NH2
1
2
3
4
C
5
(0.7 mmol)
(0.5 mmol)
OMe
OMe
OMe
X
H
N
H
N
product 5a with aniline-d7 in the presence of
1
(0.75
5
6
7
8
X
mol %)/L1 (10 mol %) did not lead to any significant deu-
terium exchange into the benzyl position of 5a under simi-
lar reaction conditions after 20 h. The significant amount
of the deuterium incorporation suggests that the imine-to-
amine hydrogenation-dehydrogenation process might
R
(91%)
(71%)
(72%)
5f X = OMe, X-ray
5g X = H
5h X = Cl
(71%)
(57%)
(70%)
(41%)
(59%)
5a
5b
5c
5d
5e
X = OMe
X = H
X = Ph
X = F
X = OMe
R = H
OMe
R = OMe
R = OMe
R = OMe
R = Cl
OMe
H
N
O
O
OMe
OMe
H
N
R
9
H
N
MeO
R
5m (75%)
10
11
12
13
14
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have occurred during the product formation of 5a
.
MeO
MeO
OMe
5l R = CH2CH2C6H4-4-OH
H
N
1.015
(51%)
R = n-hexyl
R = CH2CH2Bn
R = 2-indanyl
5i
5j
5k
(63%)
(45%)
(74%)
OMe
1 (0.75 mol %)
L1 (10 mol %)
5n
5o
5p
X = OMe
X = Cl
X = CF3
(84%)
(48%)
(37%)
N
H
NH2
X
2
OMe
(3)
C6H5Cl, 130 o
-NH3
C
OMe
OMe
N
MeO
OMe
MeO
H
N
4c
H
N
O
O
To discern the rate-limiting step of the catalytic reaction,
we employed Singleton’s high precision NMR technique to
measure the carbon isotope effect for the coupling reaction
(eq 3).19 The reaction tube of 4-methoxybenzylamine (2
N
R
H
HN
5q (70%)
(75%)
(70%)
5r (40%)
5s R = CH2CH2Ph
5t R = C6H4-4-OMe
O
N
H
O
a Reaction conditions: aniline (0.5 mmol), R-NH2 (0.7 mmol),
mol %), L1 (10 mol %), chlorobenzene (2 mL), 140 °C, 20 h.
1
(0.75
mmol) and
1
(0.75 mol %)/L1 (10 mol %) in chloroben-
zene (4 mL) was heated at 130 °C for 16 h for high conver-
sion and for 2-3 h for low conversion cases. The product 4c
was isolated by a column chromatography on silica gel,
and was analyzed by 13C NMR. The most pronounced car-
bon isotope effect was observed on the a-carbon of the
product 4c when the 13C ratio of the product at three high
conversions (86-89%) was compared with the sample
obtained at low conversions (12-15%) [(average of 13C at
87% conversion)/(average of 13C at 13% conversion) at
C(1) = 1.015(2)] (Table S2, SI).
100
80
60
40
20
0
The significant carbon isotope effect on the a-CH2 car-
bon is consistent with the C–N bond cleavage turnover-
limiting step. In support of this notion, Singleton and co-
workers showed that the observation of most pronounced
carbon isotope effect has been a definitive tool for estab-
lishing the rate-limiting step for both C–C and C–O bond
forming reactions.19c While C–N bond cleavage has been
found to be the turnover limiting step for a number of
chemical and biochemical coupling reactions,20 very few
carbon kinetic isotope effect measurements have been
reported for the catalytic coupling reactions of nitrogen
compounds. Eubanks and co-workers measured pro-
nounced carbon isotope effects in Hofmann elimination
0
50
100 150 200 250 300 350
Time (min)
Figure 1. Reaction Profile for the Coupling of 4-
Methoxybenzylamine. 4-Methoxybenzylamine (l), 4c (n)
and ArCH=NCH2Ar ().
As shown in Figure 1, the secondary amine product 4c
was formed steadily at the expense of the benzylamine
substrate. Initially, the formation of a minor product was
also observed (~10%), which gradually disappeared with-
in 200 min of the reaction time. The structure of minor
reaction
of
para-substituted
(2-phenylethyl)-
trimethylammonium bromides, which indicated an E2
mechanism involving C–N bond cleavage step.21 In a ure-
ase-catalyzed hydrolysis of hydroxyurea, Cleland and co-
workers observed the significant carbon isotope effect on
the carbonyl carbon but not on the nitrogen atom, which
argues for the formation of a common intermediate prior
to the C–N bond cleavage step.22
product
was
subsequently
determined
to
be
ArCH=NCH2Ar (Ar = 4-methoxyphenyl) by both NMR and
GC/MS, as obtained from a separate preparatory scale ex-
periment.
OMe
D
D
H
N
1 (0.75 mol %)
L1 (10 mol %)
C6H5Cl, 140 o
D
D
ND2
D
D
D
H2N
+
(2)
C
OMe
D
18% D
The Hammett plot was constructed from measuring the
rate of the coupling reaction of a series of para-substituted
benzylamines 4-X-C6H4CH2NH2 (X = OMe, Me, H, Cl, F, CF3)
D
D
5a-d
Next, we examined the deuterium labeling pattern on
the product from the reaction of aniline-d7 with 4-
methoxybenzylamine (eq 2). The reaction tube consisted
of aniline-d7 (50 mg, 0.5 mmol) with 4-
methoxybenzylamine (69 mg, 0.5 mmol) in the presence of
in the presence of (0.75 mol %)/ (10 mol %) in tolu-
ene-d8 (Figure 2). The rate of each substrate was obtained
by measuring the appearance of the product peaks, which
were normalized against an internal standard (C6Me6) as
1
L1
1
1
(7 mg, 0.75 mol %)/L1 (8 mg, 10 mol %) in chloroben-
analyzed by H NMR. The kobs for each catalytic run was
zene (1 mL) was heated in an oil bath at 140 °C for 20 h.
The product 5a-d was isolated by silica gel column chro-
determined
from
a
first
order
plot
of
ln[(benzylamine)t/(benzylamine)0] vs time. The Hammett
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The Journal of Organic Chemistry
plot of log(kX/kH) vs σp showed a linearly correlated pat- uct with the regeneration of imine species . Both the
4
6
1
2
3
4
tern with ρ = -0.79 ± 0.1. A relatively high negative slope
suggests a significant cationic character build-up on the
amine substrate during the coupling reaction.
detection of imine product and the selective deuterium
incorporation on the a-CH2 of 5a suggest that the dehydro-
genation and hydrogen transfer steps are likely facile and
reversible under the reaction conditions.
5
Conclusion
y = -0.7953x - 0.0751
6
7
8
9
R² = 0.9323
0.30
0.10
In conclusion, we successfully devised a highly chemose-
lective synthesis of secondary amines from the deamina-
tive coupling of primary amines. The catechol ligand pro-
moted ruthenium catalytic system was found to exhibit a
uniquely high activity and selectivity in forming both
symmetric and unsymmetric secondary amines. The cata-
lytic method has a number of salient features that it is op-
erationally simple, exhibits a broad substrate scope, toler-
ates common organic functional groups, and forms ammo-
nia as the sole byproduct without employing any reactive
reagents. The kinetic and spectroscopic studies thus far
indicate that the coupling reaction proceeds via the for-
mation of imine species with the turnover limiting C–N
bond cleavage step. At this time, we have not been able to
ascertain the exact role of catechol ligand on promoting
the Ru catalyst, and we are currently pursuing the detec-
tion and/or the isolation of catalytically relevant Ru-
catechol species.26 We are also devoting our efforts to ex-
tend synthetic utility of the catalytic method for the syn-
thesis of nitrogen heterocycles of biological importance.
OMe
Me
H
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
-0.10
-0.30
-0.50
Cl
F
CF3
-0.3
-0.1
0.1
0.3
0.5
sp
Figure 2. Hammett Plot from the Coupling of 4-
Methoxyaniline with 4-X-C6H4CH2NH2 (X = OMe, Me, H, Cl,
F, CF3).
PCy3
NH2
NH2
H2O
H2
N
R
R
[Ru] NH
1
[Ru]
R
R
HN
6
H
R
7
Experimental Section
NH3
General Information. All operations were carried out in a
nitrogen-filled glove box or by using standard high vacuum
and Schlenk techniques unless otherwise noted. All sol-
vents used were freshly distilled over appropriate drying
reagents. Chlorobenzene was distilled from purple solu-
tions of sodium and benzophenone, and hexanes was dried
over calcium hydride prior to use. All organic substrates
were received from commercial sources and were used
NH2
[Ru] = Ru(CO)Ln
L = amine, catechol
NH2
NH3
R
R
[Ru]
[Ru] NH
H
N
N
H
8
R
R
H
R
R
4
H
[Ru]
NH3
R
NH2
1
2
without further purification. The H, H, 13C, and 31P NMR
spectra were recorded on a Varian 400 MHz FT-NMR spec-
trometer, and the data are reported as: s = singlet, d =
doublet, t = triplet, q = quartet, m = multiplet, br = broad,
app = apparent; coupling constant(s) in Hz; integration.
Mass spectra were recorded from Agilent 6850 GC-MS
spectrometer by using a HP-5 (5% phenylmethylpolysilox-
ane) column (30 m, 0.32 mm, 0.25 µm). High resolution
mass spectra were obtained at the Mass Spectrometry/ICP
Lab, Department of Chemistry and Biochemistry, Universi-
ty of Wisconsin-Milwaukee, Milwaukee, WI. Elemental
analyses were performed at the Midwest Microlab, Indian-
apolis, IN.
N
R
R
Scheme 1. Proposed Mechanism of the Deaminative Cou-
pling of Primary Amines
We present a plausible mechanistic hypothesis for the
deaminative coupling reaction on the basis of these results
(Scheme 1). In light of the observation of imine product
ArCH=NCH2Ar, we propose the formation of a Ru-imine
species
6
as a catalytically active species, which would be
initially generated from the dehydrogenation of amine
substrate.23 In support of this notion, some oxidative C–N
bond cleavage reactions are known to proceed via the for-
mation of an imine intermediate.24 The coordination of
imine substrate to the Ru center would increase the elec-
trophilic nature of the imine carbon, and the nucleophilic
addition of the second amine substrate would proceed to
General Procedure for the Catalytic Synthesis of Second-
ary Amines. In a glove box, complex
1
(13 mg, 0.75 mol %)
and 4-(1,1-dimethylethyl)-1,2-benzenediol (L1), (16 mg,
10 mol %) were dissolved in chlorobenzene (1 mL) in a 25
mL Schlenk tube equipped with a Teflon screw cap stop-
cock and a magnetic stirring bar. The resulting mixture
was stirred for 5 to 10 minutes until the solution turned to
a reddish green color. In an alternative procedure, the
form the Ru-1,1-diamine species . Many structurally simi-
7
lar transition metal-urea complexes have been synthesized
and their bonding and reactivity patterns have been well
established.25 The observation of carbon isotope effect
provides an experimental support for the rate-limiting C–N
8
cleavage step in forming the Ru-aminoalkyl species . The
dehydrogenation of second amine substrate in conjunction
with the hydrogen transfer would form the coupling prod-
complex
2
(17 mg, 3 mol %) and L1 (16 mg, 10 mol %)
were dissolved in anhydrous 1,4-dioxane (1 mL). Amine
substrate (1.0 mmol and 1.4 mmol) in chlorobenzene (1
mL) was added to the reaction tube. After the tube was
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Page 6 of 18
sealed, it was brought out of the glove box, and was stirred 7.28–7.20 (m, 1H), 3.81 (s, 2H), 2.49 (tt, J = 10.3, 3.7 Hz,
1
2
3
4
5
6
7
8
in an oil bath maintained at 130-140 °C for 16-20 h. The
reaction tube was taken out of the oil bath, and was cooled
to room temperature. After the tube was open to air, the
solution was filtered through a short silica gel column by
eluting with CH2Cl2 (10 mL), and the filtrate was analyzed
by GC-MS. Analytically pure product was isolated by a sim-
ple column chromatography on silica gel (280-400 mesh,
hexanes/EtOAc or hexanes/EtOAc/methanol).
1H), 1.96–1.88 (m, 2H), 1.78–1.70 (m, 2H), 1.65–1.58 (m,
1H), 1.32–1.07 (m, 5H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 140.8, 128.3, 128.0, 126.7, 56.1, 51.0, 33.5, 26.1,
25.0 ppm; GC-MS for C13H19N, m/z = 189 (M+). 1H and 13
C
NMR spectral data were in good agreement with the litera-
ture values.27
N-Cyclohexyl-4-methoxybenzenemethanamine (3b).
A
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
1
Synthesis of Benzylcyclohexylamine (3a). In a glove box,
mol %), L1 (16 mg, 10 mol %), 4-methoxybenzylamine
(137 mg, 1.0 mmol) and cyclohexylamine (139 mg, 1.4
mmol) was stirred at 130 °C for 16 h. The product 3b was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 171 mg, 78%). TLC; Rf =
9
complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol %)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
were dissolved in chlorobenzene (1 mL) in a 25 mL
Schlenk tube equipped with a Teflon screw cap stopcock
and a magnetic stirring bar. The resulting mixture was
stirred for 5-10 min until the solution was turned reddish
green color. Benzylamine (1.0 mmol) and cyclohexylamine
(1.4 mmol) were dissolved in chlorobenzene (1 mL), and
the solution was added to the reaction tube. The tube was
brought out of the glove box, and was stirred in an oil bath
maintained at 130 °C for 16 h. The reaction tube was taken
out of the oil bath, and was cooled to room temperature.
The resulting solution was filtered through a short silica
gel column by eluting with CH2Cl2 (10 mL), and the filtrate
was analyzed by GC-MS. Analytically pure product 3a was
isolated by a simple column chromatography on silica gel
(280-400 mesh, n-hexane/EtOAc).
0.3 (20% EtOAc in hexanes). Data for 3b:
1HNMR (400
MHz, CDCl3) δ 7.25–7.21 (m, 2H), 6.88–6.83 (m, 2H), 3.79
(s, 3H), 3.74 (s, 2H), 2.47 (tt, J = 10.4, 3.7 Hz, 1H), 1.96–
1.86 (m, 2H), 1.77–1.68 (m, 2H), 1.65– 1.56 (m, 1H), 1.31
(br s, 1H), 1.30–1.05 (m, 5H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 158.4, 133.0, 129.2, 113.7, 56.0, 55.2, 50.4, 33.5,
1
26.1, 25.0 ppm; GC-MS for C14H21NO, m/z = 219 (M+). H
and 13C NMR spectral data were in good agreement with
the literature values.28
N-Cyclohexyl-4-fluorobenzenemethanamine (3c).
A
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
1
mol %), L1 (16 mg, 10 mol %), 4-fluorobenzylamine (125
mg, 1.0 mmol) and cyclohexylamine (139 mg, 1.4 mmol)
was stirred at 130 °C for 16 h. The product 3c was isolated
Synthesis of Dibenzylamine (4a). In a glove box, complex
(13 mg, 0.75 mol %) and L1 (16 mg, 10 mol %) were
1
dissolved in chlorobenzene (1 mL) in a 25 mL Schlenk tube
equipped with a Teflon screw cap stopcock and a magnetic
stirring bar. The resulting mixture was stirred for 5 to 10
min until the solution was turned reddish green color.
Benzylamine (107 mg, 1.0 mmol) in chlorobenzene (1 mL)
was added to the reaction mixture. After the tube was
sealed, it was brought out of the glove box, and was stirred
in an oil bath maintained at 130 °C for 16 h. The reaction
tube was taken out of the oil bath, and was cooled to room
temperature. The resulting solution was filtered through a
short silica gel column by eluting with CH2Cl2 (10 mL), and
the filtrate was analyzed by GC-MS. Analytically pure
product 4a was isolated by a simple column chromatog-
raphy on silica gel (280-400 mesh, n-hexane/EtOAc).
by
a
column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 147 mg, 71%). TLC; Rf =
0.4 (20% EtOAc in hexanes). Data for 3c: H NMR (400
1
MHz, CDCl3) δ 7.31–7.23 (m, 2H), 7.02–6.95 (m, 2H), 3.76
(s, 2H), 2.45 (tt, J = 10.3, 3.8 Hz, 1H), 1.94–1.85 (m, 2H),
1.77–1.68 (m, 2H), 1.64–1.56 (m, 1H), 1.37 (br s, 1H),
1.32–1.04 (m, 6H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
161.7 (d, JCF = 244.2 Hz), 136.6 (d, JCF = 3.1 Hz), 129.5 (d,
JCF = 7.9 Hz), 115.1 (d, JCF = 21.2 Hz), 56.1, 50.2, 33.5, 26.1,
24.9 ppm; GC-MS for C13H18FN, m/z = 207 (M+). 1H and 13
NMR spectral data were in good agreement with the litera-
ture values.29
C
N-Cyclohexyl-4-(trifluoromethyl)benzenemethanamine
(3d). A chlorobenzene (2.0 mL) solution of complex
1
(13
Catalyst and Ligand Screening Study. In a glove box, a Ru
catalyst (3 mol % Ru atom) and a ligand (10 mol %) were
dissolved in a solvent (1 mL) in a 25 mL Schlenk tube
equipped with a Teflon screw cap stopcock and a magnetic
stirring bar. After stirring for 5 to 10 min, benzylamine (54
mg, 0.5 mmol) and cyclohexylamine (69 mg, 0.7 mmol)
were dissolved in chlorobenzene (1 mL), and the solution
was added to the reaction tube. The tube was brought out
of the glove box, and was stirred in an oil bath at 130 °C for
mg, 0.75 mol %), L1 (16 mg, 10 mol %), 4-
trifluromethylbenzylamine (175 mg, 1.0 mmol) and cyclo-
hexylamine (139 mg, 1.4 mmol) was stirred at 130 °C for
16 h. The product 3d was isolated by a column chromatog-
raphy on silica gel (n-hexane/EtOAc = 100:1 to 10:1; 152
mg, 59%). TLC; Rf = 0.4 (20% EtOAc in hexanes). Data for
1
3d: H NMR (400 MHz, CDCl3) δ 7.58–7.53 (m, 2H), 7.45–
7.41 (m, 2H), 3.86 (s, 2H), 2.46 (tt, J = 10.3, 3.7 Hz, 1H),
1.95–1.86 (m, 2H), 1.77–1.69 (m, 2H), 1.64–1.56 (m, 1H),
1.30–1.05 (m, 5H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
145.1, 129.0 (q, JCF = 32.2 Hz), 128.2, 125.2 (q, JCF = 3.8
Hz), 124.3 (q, JCF = 271.9 Hz), 56.2, 50.4, 33.5, 26.0, 24.9
1
16 h. The product yield was determined by H NMR by
using hexamethylbenzene as an internal standard. The
results are summarized in Table S1 and S2.
1
ppm; GC-MS for C14H18F3N, m/z = 257 (M+). H and 13C
N-Cyclohexylbenzenemethanamine (3a). A chloroben-
NMR spectral data were in good agreement with the litera-
zene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol %),
ture values.30
L1 (16 mg, 10 mol %), benzylamine (107 mg, 1.0 mmol)
and cyclohexylamine (139 mg, 1.4 mmol) was stirred at
130 °C for 16 h. The product 3a was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 138 mg, 73%). TLC; Rf = 0.3 (10% EtOAc in hexanes).
Data for 3a: 1H NMR (400 MHz, CDCl3) δ 7.35–7.29 (m, 4H),
N-(4-Chlorobenzyl)-2-(4-methoxyphenyl)ethanamine
(3e). A chlorobenzene (2.0 mL) solution of complex
1
(13
mg, 0.75 mol %), L1 (16 mg, 10 mol %), 4-
chlorobenzylamine (141 mg, 1.0 mmol) and 4-
methoxybenzeneethanamine (211 mg, 1.4 mmol) was
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The Journal of Organic Chemistry
stirred at 130 °C for 16 h. The product 3e was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
Ethyl 3-(benzylamino)propanoate (3i). A chlorobenzene
(2.0 mL) solution of complex (13 mg, 0.75 mol %), L1
1
2
3
4
5
6
7
8
1
100:1 to 10:1; 158 mg, 57%). TLC; Rf = 0.4 (20% EtOAc in
(16 mg, 10 mol %), β-alanine ethyl ester (117 mg, 1.0
mmol) and benzylamine (150 mg, 1.4 mmol) was stirred at
130 °C for 16 h. The product 3i was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 149 mg, 72%). TLC; Rf = 0.3 (20% EtOAc in hexanes).
Data for 3i: 1HNMR (400 MHz, CDCl3) δ 7.33–7.19 (m, 5H),
4.11 (q, J = 7.2 Hz, 2H), 3.78 (s, 2H), 2.87 (t, J = 6.5 Hz,
2H), 2.50 (t, J = 6.5 Hz, 2H), 1.82 (brs, 1H), 1.23 (t, J = 7.2
Hz, 3H), ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 172.7,
140.0, 128.3, 128.0, 126.8, 60.3, 53.7, 44.4, 34.7, 14.1 ppm;
1
hexanes). Data for 3e: HNMR (400 MHz, CDCl3) δ 7.30–
7.25 (m, 2H), 7.24–7.19 (m, 2H), 7.15–7.09 (m, 2H), 6.87–
6.82 (m, 2H), 3.79 (s, 3H), 3.76 (s, 2H), 2.87–2.82 (m, 2H),
2.80–2.74 (m, 2H), 1.73 (br s, 1H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 157.9, 138.6, 132.5, 131.7, 129.5, 129.3,
128.4, 113.8, 55.1, 53.0, 50.5, 35.2 ppm; GC-MS for
C16H18ClNO, m/z = 275 (M+). HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C16H18ClNOH 276.1150; Found 276.1122.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N-(Biphenyl-4-ylmethyl)hexan-1-amine (3f). A chloro-
1
GC-MS for C12H17NO2, m/z = 207 (M+). H and 13C NMR
benzene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol
spectral data were in good agreement with the literature
values.31
%), L1 (16 mg, 10 mol %), 4-pheylbenzylamine (183 mg,
1.0 mmol) and 1-hexamine (141 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3f was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 176 mg, 66%). TLC; Rf = 0.3 (20% EtOAc in
4-Fluoro-N-hexylbenzenemethanamine (3j). A chloro-
benzene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol
%), L1 (16 mg, 10 mol %), 4-flurobenzylamine (125 mg,
1.0 mmol) and 1-hexamine (141 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3j was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 132 mg, 63%). TLC; Rf = 0.3 (20% EtOAc in
1
hexanes). Data for 3f: HNMR (400 MHz, CDCl3) δ 7.61–
7.54 (m, 4H), 7.46–7.37 (m, 4H), 7.36–7.31 (m, 1H), 3.83
(s, 2H), 2.66 (t, J = 7.3 Hz, 2H), 1.58–1.50 (m, 2H), 1.36–
1.26 (m, 6H), 0.89 (t, J = 7.0 Hz, 3H) ppm; 13C{1H} NMR
(100 MHz, CDCl3) δ 141.0, 139.8, 139.6, 128.7, 128.5,
128.4, 127.1, 127.0, 53.7, 49.6, 31.8, 30.1, 27.0, 22.6, 14.1
ppm; GC-MS for C19H25N, m/z = 267 (M+); HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C19H25NH 268.2060; Found
268.2061.
1
hexanes). Data for 3j: HNMR (400 MHz, CDCl3) δ 7.30–
7.24 (m, 2H), 7.02–6.95 (m, 2H), 3.74 (s, 2H), 2.59 (t, J =
7.3, 2H), 1.53–1.44 (m, 2H), 1.35–1.21 (m, 6H), 0.90–0.84
(m, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 161.8 (d, JCF
= 244.6 Hz), 136.2 (d, JCF = 3.1 Hz), 129.6 (d, JCF = 7.9 Hz),
115.0 (d, JCF = 21.2 Hz), 53.3, 49.4, 31.7, 30.0, 27.0, 22.6,
14.0 ppm; GC-MS for C13H20FN, m/z = 209 (M+); HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C13H20FNH 210.1653;
Found 260.1654.
Benzo[d][1,3]dioxol-5-yl-N-(biphenyl-4-
ylmethyl)methanamine (3g). A chlorobenzene (2.0 mL)
solution of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10
mol %), 4-pheylbenzylamine (183 mg, 1.0 mmol) and 1,3-
benzodioxol-5-ylmethylamine (211 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3g was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 178 mg, 56%). TLC; Rf = 0.3 (20% EtOAc in
N-(4-fluorobenzyl)-N-(4-methoxybenzyl)amine (3k).
A
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
1
mol %), L1 (16 mg, 10 mol %), 4-flurobenzylamine (125
mg, 1.0 mmol) and 4-methoxybenzylamine (192 mg, 1.4
mmol) was stirred at 130 °C for 16 h. The product 3k was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 162 mg, 66%). TLC; Rf =
1
hexanes). Data for 3g: HNMR (400 MHz, CDCl3) δ 7.62–
7.55 (m, 4H), 7.47–7.39 (m, 4H), 7.37–7.32 (m, 1H), 6.90–
6.88 (m, 1H), 6.82–6.76 (m, 2H), 5.95 (s, 2H), 3.84 (s, 2H),
3.75 (s, 2H), 1.67 (br s, 1H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 147.7, 146.5, 140.9, 139.9, 139.3, 134.2, 128.7,
128.6, 127.1, 127.1, 127.0, 121.2, 108.7, 108.0, 100.9, 52.9,
52.6 ppm; GC-MS for C21H19NO2, m/z = 317 (M+); HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C21H19NO2H 318.1489,
Found 318.1486.
1
0.3 (20% EtOAc in hexanes). Data for 3k: H NMR (400
MHz, CDCl3) δ 7.35–7.29 (m, 2H), 7.27 (d, J = 8.3 Hz, 2H),
7.06–6.99 (m, 2H), 6.90 (d, J = 8.3 Hz, 2H), 3.81 (s, 3H),
3.76 (s, 2H), 3.74 (s, 2H), 1.78 (br s, 1H) ppm; 13C{1H} NMR
(100 MHz, CDCl3) δ 161.8 (d, JCF = 244.6 Hz), 158.5, 135.9
(d, JCF = 3.1 Hz), 132.1, 129.6 (d, JCF = 7.9 Hz), 129.2, 115.0
(d, JCF = 21.2 Hz), 113.7, 55.1, 52.4, 52.1; GC-MS for
C15H16FNO, m/z = 245 (M+). 1H and 13C NMR spectral data
were in good agreement with the literature values.32
N-(4-(Trifluoromethyl)benzyl)hexan-1-amine (3h).
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
mol %), (16 mg, 10 mol %), 4-
L1
A
1
trifluromethylbenzylamine (175 mg, 1.0 mmol) and 1-
hexamine (141 mg, 1.4 mmol) was stirred at 130 °C for 16
h. The product 3h was isolated by a column chromatog-
raphy on silica gel (n-hexanes/EtOAc = 100:1 to 10:1; 142
mg, 55%). TLC; Rf = 0.4 (20% EtOAc in hexanes). Data for
N-[(4-fluorophenyl)methyl]-4-methoxy-
benzeneethanamine (3l). A chlorobenzene (2.0 mL) solu-
tion of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol
%), 4-flurobenzylamine (125 mg, 1.0 mmol) and 4-
methoxybenzeneethanamine (211 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3l was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 142 mg, 55%). TLC; Rf = 0.3 (20% EtOAc in
1
3h: H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 8.2 Hz, 2H),
7.44 (d, J = 8.2 Hz, 2H), 3.84 (s, 2H), 2.61 (t, J = 7.2 Hz,
2H), 1.58 (br s, 1H), 1.55–1.46 (m, 2H), 1.37–1.22 (m, 6H),
0.91–0.84 (m, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
144.6, 129.1 (q, JCF = 32.3 Hz), 128.3, 125.3 (q, JCF = 3.8
Hz), 124.2 (q, JCF = 272.0 Hz), 53.5, 49.5, 31.7, 30.0, 27.0,
22.6, 14.0; GC-MS for C14H20F3N, m/z = 259 (M+); HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C14H20F3NH 260.1621;
Found 260.1627.
1
hexanes). Data for 3l: H NMR (400 MHz, CDCl3) δ 7.27–
7.21 (m, 2H), 7.15–7.10 (m, 2H), 7.03–6.96 (m, 2H), 6.87–
6.82 (m, 2H), 3.79 (s, 3H), 3.76 (s, 2H), 2.88–2.83 (m, 2H),
2.80–2.74 (m, 2H), 1.69 (br s, 1H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 161.8 (d, JCF = 244.6 Hz), 157.9, 135.8 (d, JCF
= 3.1 Hz), 131.8, 129.5, 129.5 (d, JCF = 7.9 Hz), 115.0 (d, JCF
= 21.2 Hz), 113.8, 55.1, 53.0, 50.6, 35.2 ppm; GC-MS for
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 18
C16H18FNO, m/z = 259 (M+); HRMS (ESI-TOF) m/z:
2.74–2.68 (m, 2H), 2.39 (tt, J = 10.6, 3.8 Hz, 1H), 1.88–1.78
[M+H]+ Calcd for C16H18FNOH 260.1445; Found 260.1439.
1
2
3
4
5
6
7
8
(m, 2H), 1.74–1.64 (m, 2H), 1.62–1.54 (m, 1H), 1.48 (br s,
1H), 1.29–0.95 (m, 5H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 157.8, 132.0, 129.4, 113.7, 56.6, 55.0, 48.3, 35.5,
33.4, 26.0, 24.9 ppm; GC-MS for C15H23NO, m/z = 233 (M+);
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C15H23NOH
234.1852; Found 234.1854.
N-[(4-Fluorophenyl)methyl]-β-
methylbenzeneethanamine (3m). A chlorobenzene (2.0
mL) solution of complex
1
(13 mg, 0.75 mol %), L1 (16 mg,
10 mol %), 4-flurobenzylamine (125 mg, 1.0 mmol) and β-
methylphenethylamine (189 mg, 1.4 mmol) was stirred at
130 °C for 16 h. The product 3m was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 141 mg, 58%). TLC; Rf = 0.4 (20% EtOAc in hexanes).
N-(4-Methoxyphenethyl)-2,3-dihydro-1H-inden-2-
amine (3q). A chlorobenzene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol %), 4-
9
1
Data for 3m: H NMR (400 MHz, CDCl3) δ 7.37–7.30 (m,
methoxybenzeneethanamine (151 mg, 1.0 mmol) and 2-
aminoindane (186 mg, 1.4 mmol) was stirred at 130 °C for
16 h. The product 3q was isolated by a column chromatog-
raphy on silica gel (n-hexane/EtOAc = 100:1 to 10:1; 144
mg, 54%). TLC; Rf = 0.3 (20% EtOAc in hexanes). Data for
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2H), 7.26–7.19 (m, 5H), 7.03–6.96 (m, 2H), 3.74 (ABq, J =
13.5 Hz, 2H), 2.99 (qt, J = 7.1, 7.0 Hz, 1H), 2.84–2.77 (m,
2H), 1.55 (br s, 1H), 1.28 (d, J = 7.0 Hz, 3H) ppm; 13C{1H}
NMR (100 MHz, CDCl3) δ 161.7 (d, JCF = 244.2 Hz), 145.1,
135.8 (d, JCF = 3.1 Hz), 129.4 (d, JCF = 7.9 Hz), 128.5, 127.1,
126.3, 115.0 (d, JCF = 21.2 Hz), 56.1, 52.9, 39.9, 20.0 ppm;
GC-MS for C16H18FN, m/z = 243 (M+); HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C16H18FNH 244.1496; Found
244.1500.
1
3q: H NMR (400 MHz, CDCl3) δ 7.22–7.12 (m, 6H), 6.89–
6.83 (m, 2H), 3.80 (s, 3H), 3.65 (quintet, J = 7.0 Hz, 1H),
3.17 (dd, J = 7.2 Hz, 2H), 2.96–2.90 (m, 2H), 2.82–2.70 (m,
4H), 1.67 (br s, 1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
158.0, 141.6, 131.9, 129.5, 126.3, 124.6, 113.9, 59.5, 55.2,
49.7, 39.9, 35.5 ppm; GC-MS for C18H21NO, m/z = 267 (M+);
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C18H21NOH
268.1696; Found 268.1699.
4-Methoxy-N-(phenylmethyl)benzeneethanamine (3n).
A chlorobenzene (2.0 mL) solution of complex
1
(13 mg,
0.75 mol %), L1 (16 mg, 10 mol %), 4-
methoxybenzeneethanamine (151 mg, 1.0 mmol) and ben-
zylamine (150 mg, 1.4 mmol) was stirred at 130 °C for 16
h. The product 3n was isolated by a column chromatog-
raphy on silica gel (n-hexane/EtOAc = 100:1 to 10:1; 169
mg, 70%). TLC; Rf = 0.3 (10% EtOAc in hexanes). Data for
3n: 1H NMR (400 MHz, CDCl3) δ 7.37–7.23 (m, 5H), 7.15 (d,
J = 8.3 Hz, 2H), 6.86 (d, J = 8.3 Hz, 2H), 3.82 (s, 2H), 3.80
(s, 3H), 2.89 (t, J = 6.9 Hz, 2H), 2.80 (t, J = 6.9 Hz, 2H), 1.66
(br s, 1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 157.9,
140.1, 131.9, 129.5, 128.3, 128.0, 126.8, 113.8, 55.1, 53.8,
N-(4-Methoxyphenethyl)-1-(4-
methoxyphenyl)ethanamine (3r). A chlorobenzene (2.0
mL) solution of complex
1
(13 mg, 0.75 mol %), L1 (16 mg,
10 mol %), 4-methoxybenzeneethanamine (151 mg, 1.0
mmol) and (R)-(+)-1-(4-methoxyphenyl)ethylamine (211
mg, 1.4 mmol) was stirred at 130 °C for 16 h. The product
3r was isolated by a column chromatography on silica gel
(n-hexane/EtOAc = 100:1 to 10:1; 186 mg, 65%). TLC; Rf
1
= 0.3 (20% EtOAc in hexanes). Data for 3r: H NMR (400
MHz, CDCl3) δ 7.21–7.15 (m, 2H), 7.10–7.05 (m, 2H), 6.87–
6.79 (m, 4H), 3.79 (s, 3H), 3.78 (s, 3H), 3.73 (q, J = 6.6 Hz,
1H), 2.79–2.60 (m, 4H), 1.86 (br s, 1H), 1.32 (d, J = 6.6,
3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 158.3, 157.8,
137.4, 131.9, 129.4, 127.4, 113.7, 113.6, 57.4, 55.0, 48.9,
35.2, 24.1 ppm (one carbon signal obscured or overlap-
ping); GC-MS for C18H23NO2, m/z = 285 (M+); HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C18H23NO2H 286.1802; Found
286.1798.
1
50.6, 35.3 ppm; GC-MS for C16H19NO, m/z = 241 (M+). H
and 13C NMR spectral data were in good agreement with
the literature values.33
N-(4-Methoxyphenethyl)hexan-1-amine (3o). A chloro-
benzene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol
%), L1 (16 mg, 10 mol %), 4-methoxybenzeneethanamine
(151 mg, 1.0 mmol) and 1-hexamine (141 mg, 1.4 mmol)
was stirred at 130 °C for 16 h. The product 3o was isolated
by
a
column chromatography on silica gel (n-
N-(4-Methoxyphenethyl)-4-phenylbutan-2-amine (3s).
1
A chlorobenzene (2.0 mL) solution of complex (13 mg,
hexane/EtOAc = 100:1 to 10:1; 119 mg, 51%). TLC; Rf =
1
0.3 (10% EtOAc in hexanes). Data for 3o: H NMR (400
0.75 mol %), L1 (16 mg, 10 mol %), 4-
methoxybenzeneethanamine (151 mg, 1.0 mmol) and
(±)1-methyl-3-phenyl-1-propanamine (209 mg, 1.4
mmol) was stirred at 130 °C for 16 h. The product 3s was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 208 mg, 73%. TLC; Rf = 0.3
MHz, CDCl3) δ 7.12 (d, J = 8.7 Hz, 2H), 6.83 (d, J = 8.7 Hz,
2H), 3.78 (s, 3H), 2.86–2.81 (m, 2H), 2.78–2.72 (m, 2H),
2.62–2.57 (m, 2H), 1.68 (br s, 1H), 1.50–1.41 (m, 2H),
1.33–1.23 (m, 6H), 0.89–0.84 (m, 3H) ppm; 13C{1H} NMR
(100 MHz, CDCl3) δ 157.9, 132.0, 129.6, 113.8, 55.2, 51.4,
49.9, 35.3, 31.7, 29.9, 27.0, 22.6, 14.0 ppm; GC-MS for
C15H25NO, m/z = 235 (M+); HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C15H25NOH 236.2009; Found 236.2005.
1
(20% EtOAc in hexanes). Data for 3s: H NMR (400 MHz,
CDCl3) δ 7.30–7.25 (m, 2H), 7.21–7.11 (m, 5H), 6.88–6.83
(m, 2H), 3.79 (s, 3H), 2.94–2.84 (m, 1H), 2.82–2.70 (m,
3H), 2.70–2.52 (m, 3H), 1.82–1.72 (m, 1H), 1.66–1.56 (m,
1H), 1.54 (br s, 1H), 1.10 (d, J = 6.3 Hz, 3H) ppm; 13C{1H}
NMR (100 MHz, CDCl3) δ 157.9, 142.2, 132.0, 129.6, 128.3,
128.2, 125.6, 113.8, 55.2, 52.4, 48.5, 38.5, 35.5, 32.2, 20.2
ppm; GC-MS for C19H25NO, m/z = 283 (M+); HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C19H25NOH 284.2009; Found
284.2010.
N-Cyclohexyl-4-methoxybenzeneethanamine (3p).
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
mol %), (16 mg, 10 mol %), 4-
L1
A
1
methoxybenzeneethanamine (151 mg, 1.0 mmol) and cy-
clohexylamine (139 mg, 1.4 mmol) was stirred at 130 °C
for 16 h. The product 3p was isolated by a column chroma-
tography on silica gel (n-hexanes/EtOAc = 100:1 to 10:1;
187 mg, 80%). TLC; Rf = 0.3 (20% EtOAc in hexanes). Data
for 3p: 1H NMR (400 MHz, CDCl3) δ 7.10 (d, J = 8.7 Hz, 2H),
6.81 (d, J = 8.7 Hz, 2H), 3.75 (s, 3H), 2.86–2.81 (m, 2H),
4-Methoxy-N-[(4-
methoxyphenyl)methyl]benzeneethanamine (3t). A chlo-
robenzene (2.0 mL) solution of complex
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(13 mg, 0.75

Page 9 of 18
The Journal of Organic Chemistry
mol
%),
L1
(16
mg,
10
mol
%),
4-
1H), 1.95–1.84 (m, 2H), 1.77–1.67 (m, 2H), 1.64–1.54 (m,
1H), 1.30–1.04 (m, 5H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 147.6, 146.3, 134.8, 121.1, 108.6, 108.0, 100.8,
55.9, 50.7, 33.4, 26.1, 24.9 ppm; GC-MS for C14H19NO2, m/z
1
2
3
4
5
6
7
8
methoxybenzeneethanamine (151 mg, 1.0 mmol) and 4-
methoxybenzylamine (192 mg, 1.4 mmol) was stirred at
130 °C for 16 h. The product 3t was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 149 mg, 55%). TLC; Rf = 0.3 (20% EtOAc in hexanes).
Data for 3t: 1H NMR (400 MHz, CDCl3) δ 7.21 (d, J = 8.3 Hz,
2H), 7.13 (d, J = 8.3 Hz, 2H), 6.90–6.82 (m, 4H), 3.80 (s,
3H), 3.79 (s, 3H), 3.75 (s, 2H), 2.87 (t, J = 7.1 Hz, 2H), 2.78
(t, J = 7.1 Hz, 2H), 1.71 (br s, 1H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 158.5, 157.9, 132.3, 131.9, 129.5, 129.2,
113.7, 113.6, 55.1, 55.1, 53.2, 50.6, 35.2 ppm; GC-MS for
C17H21NO2, m/z = 271 (M+). 1H and 13C NMR spectral data
were in good agreement with the literature values.33
1
= 233 (M+). H and 13C NMR spectral data were in good
agreement with the literature values.34
N-(Benzo[d][1,3]dioxol-5-ylmethyl)-1-(4-
methoxyphenyl)ethanamine (3x). A chlorobenzene (2.0
mL) solution of complex
10 mol %), 1-(1,3-benzodioxol-5-yl)methanamine (151
mg, 1.0 mmol) and (R)-(+)-1-(4-
1
(13 mg, 0.75 mol %), L1 (16 mg,
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
methoxyphenyl)ethylamine (211 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3x was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 171 mg, 60%). TLC; Rf = 0.3 (20% EtOAc in
N-(3-Fluorophenethyl)-2,3-dihydro-1H-inden-2-amine
(3u). A chlorobenzene (2.0 mL) solution of complex
1
1
(13
hexanes). Data for 3x: H NMR (400 MHz, CDCl3) δ 7.30–
mg, 0.75 mol %), L1 (16 mg, 10 mol %), 2-(3-
fluorophenyl)ethylamine (139 mg, 1.0 mmol) and 2-
aminoindane (186 mg, 1.4 mmol) was stirred at 130 °C for
16 h. The product 3u was isolated by a column chromatog-
raphy on silica gel (n-hexane/EtOAc = 100:1 to 10:1; 193
mg, 76%). TLC; Rf = 0.4 (10% EtOAc in hexanes). Data for
7.24 (m, 2H), 6.93–6.86 (m, 2H), 6.82–6.78 (m, 1H), 6.77–
6.67 (m, 2H), 5.93 (s, 2H), 3.82 (s, 3H), 3.76 (q, J = 6.6 Hz,
1H), 3.52 (ABq, J = 13.2 Hz, 2H), 1.70 (br s, 1H), 1.34 (d, J
= 6.6 Hz, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 158.5,
147.6, 146.3, 137.4, 134.5, 127.7, 121.1, 113.8, 108.7,
108.0, 100.8, 56.5, 55.2, 51.3, 24.4 ppm; GC-MS for
C17H19NO3, m/z = 285 (M+); HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C17H19NO3H 286.1438; Found 286.1427.
1
3u: H NMR (400 MHz, CDCl3) δ 7.3–7.24 (m, 1H), 7.24–
7.12 (m, 4H), 7.06–7.00 (m, 1H), 6.99–6.89 (m, 2H), 3.67
(quintet, J = 6.9 Hz, 1H), 3.18 (dd, J = 15.5, 7.2 Hz, 2H),
3.01–2.92 (m, 2H), 2.89–2.81 (m, 2H), 2.75 (dd, J = 15.5,
6.6 Hz, 2H), 1.63 (br s, 1H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 162.8 (d, JCF = 245.5 Hz), 142.5 (d, JCF = 7.2 Hz),
N-(Benzo[d][1,3]dioxol-5-ylmethyl)-2-(4-
methoxyphenyl)propan-1-amine (3y). A chlorobenzene
(2.0 mL) solution of complex
(16 mg, 10 mol %), 1-(1,3-benzodioxol-5-yl)methanamine
(151 mg, 1.0 mmol) and (±)-1-(4-
1
(13 mg, 0.75 mol %), L1
141.5, 129.8 (d, JCF = 8.3 Hz), 126.4, 124.6, 124.3 (d, JCF
=
2.7 Hz), 115.4 (d, JCF = 20.8 Hz), 113.0 (d, JCF = 21.0 Hz),
59.4, 49.2, 39.9, 36.2 (d, JCF = 1.6 Hz) ppm; GC-MS for
C17H18FN, m/z = 255 (M+); HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C17H18FNH 256.1496; Found 256.1501.
methoxyphenyl)ethylamine (211 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3y was isolated by a
column chromatography on silica gel (n-hexanes/EtOAc =
100:1 to 10:1; 152 mg, 56%). TLC; Rf = 0.3 (20% EtOAc in
1
N-(3-Fluorophenethyl)-1-(4-
methoxyphenyl)ethanamine (3v). A chlorobenzene (2.0
mL) solution of complex
10 mol %), 2-(3-fluorophenyl)ethylamine (139 mg, 1.0
mmol) and (R)-(+)-1-(4-methoxyphenyl)ethylamine (211
mg, 1.4 mmol) was stirred at 130 °C for 16 h. The product
3v was isolated by a column chromatography on silica gel
(n-hexane/EtOAc = 100:1 to 10:1; 157 mg, 58%). TLC; Rf
hexanes). Data for 3y: H NMR (400 MHz, CDCl3) δ 7.35–
7.28 (m, 2H), 7.24–7.18 (m, 3H), 6.75 (d, J = 1.6 Hz, 2H),
6.73 (d, J = 7.9 Hz, 1H), 6.68 (dd, J = 7.9, 1.6 Hz, 1H), 5.93
(s, 2H), 3.66 (ABq, J = 13.2 Hz, 2H), 2.96 (sextet, J = 7.1 Hz,
1H), 2.77 (d, J = 7.2 Hz, 2H), 1.66 (br s, 1H), 1.26 (d, J = 7.1
Hz, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 147.6,
146.4, 145.2, 134.1, 128.5, 127.2, 126.4, 121.1, 108.6,
108.0, 100.8, 56.0, 53.5, 39.9, 20.1 ppm; GC-MS for
C17H19NO2, m/z = 269 (M+); HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C17H19NO2H 270.1489; Found 270.1463.
1
(13 mg, 0.75 mol %), L1 (16 mg,
1
= 0.3 (20% EtOAc in hexanes). Data for 3v: H NMR (400
MHz, CDCl3) δ 7.27–7.16 (m, 3H), 6.98–6.80 (m, 5H), 3.80
(s, 3H), 3.73 (q, J = 6.6 Hz, 1H), 2.83–2.63 (m, 4H), 1.60 (br
s, 1H), 1.32 (d, J = 6.6 Hz, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 162.8 (d, JCF = 245.4 Hz), 158.5, 142.6 (d, JCF
= 7.2 Hz), 137.3, 129.7 (d, JCF = 8.3 Hz), 127.5, 124.3 (d, JCF
N-Hexyl-1,2,3,4-tetrahydro-1-naphthalenamine (3z).
A
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
1
mol %), L1 (16 mg, 10 mol %), 1,2,3,4-tetrahydro-1-
naphthalenamine (147 mg, 1.0 mmol) 1-hexamine (141
mg, 1.4 mmol) was stirred at 130 °C for 16 h. The product
3z was isolated by a column chromatography on silica gel
(n-hexane/EtOAc = 100:1 to 10:1; 106 mg, 46%). TLC; Rf
= 2.7 Hz), 115.4 (d, JCF = 20.9 Hz), 113.7, 112.9 (d, JCF
=
21.0 Hz), 57.5, 55.2, 48.5, 36.1 (d, JCF = 1.7 Hz), 24.2 ppm;
GC-MS for C17H20FNO, m/z = 273 (M+); HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C17H20FNOH 274.1602; Found
274.1604.
1
= 0.3 (10% EtOAc in hexanes). Data for 3z: H NMR (400
MHz, CDCl3) 7.37–7.30 (m, 1H), 7.21–7.05 (m, 3H), 3.77 (t,
J = 4.8 Hz, 1H), 2.87–2.61 (m, 1H), 2.03–1.91 (m, 1H),
1.91–1.81 (m, 2H), 1.78–1.68 (m, 1H), 1.56–1.46 (m, 2H),
1.41–1.19 (m, 7H), 0.94–0.85 (m, 3H) ppm; 13C{1H} NMR
(100 MHz, CDCl3) δ 139.3, 137.3, 129.0, 128.7, 126.5,
125.6, 55.4, 47.3, 31.8, 30.4, 29.3, 28.2, 27.1, 22.6, 18.9,
14.1 ppm; GC-MS for C16H25N, m/z = 231 (M+); HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C16H25NH 232.2060; Found
232.2053.
N-Cyclohexyl-1,3-benzodioxole-5-methanamine (3w).
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
A
1
mol %), L1 (16 mg, 10 mol %), 1-(1,3-benzodioxol-5-
yl)methanamine (151 mg, 1.0 mmol) and cyclohexylamine
(139 mg, 1.4 mmol) was stirred at 130 °C for 16 h. The
product 3w was isolated by a column chromatography on
silica gel (n-hexane/EtOAc = 100:1 to 10:1; 138 mg, 59%).
TLC; Rf = 0.3 (20% EtOAc in hexanes). Data for 3w: H
NMR (400 MHz, CDCl3) δ 6.83–6.81 (m, 1H), 6.75–6.73 (m,
2H), 5.92 (s, 2H), 3.70 (s, 2H), 2.45 (tt, J = 10.4, 3.8 Hz,
1
N-[2-(4-Methoxyphenyl)ethyl]-1,2,3,4-tetrahydro-1-
naphthalenamine (3aa). A chlorobenzene (2.0 mL) solu-
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Page 10 of 18
tion of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol
25.9, 25.0 ppm; GC-MS for C14H21NO, m/z = 219 (M+);
Anal. Calcd for C14H21NO: C, 76.67; H, 9.65. Found: C, 76.78;
H, 9.35; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C14H21NOH 220.1696; Found 220.1698.
1
2
3
4
5
6
7
8
%), 1,2,3,4-tetrahydro-1-naphthalenamine (147 mg, 1.0
mmol) and 4-methoxybenzeneethanamine (211 mg, 1.4
mmol) was stirred at 130 °C for 16 h. The product 3aa was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 177 mg, 63%). TLC; Rf =
Dibenzylamine (4a). A chlorobenzene (2.0 mL) solution
of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol %)
1
0.3 (10% EtOAc in hexanes). Data for 3aa: H NMR (400
and benzylamine (107 mg, 1.0 mmol) was stirred at 130 °C
for 16 h. The product 4a was isolated by a column chroma-
tography on silica gel (n-hexane/EtOAc = 100:1 to 10:1;
88 mg, 89%). TLC; Rf = 0.3 (10% EtOAc in hexanes). Data
for 4a: 1H NMR (400 MHz, CDCl3) 7.42–7.24 (m, 10H), 3.84
(s, 4H), 2.08 (br s, 1H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 140.0, 128.4, 128.1, 126.9, 53.0 ppm; GC-MS for
MHz, CDCl3) δ 7.28–7.23 (m, 1H), 7.21–7.13 (m, 4H), 7.12–
7.07 (m, 1H), 6.90–6.85 (m, 2H), 3.82 (s, 3H), 3.81 (t, J =
4.7 Hz, 1H), 3.05–2.89 (m, 2H), 2.87–2.69 (m, 4H), 2.01–
1.86 (m, 3H), 1.80–1.70 (m, 1H), 1.63 (br s, 1H) ppm;
13C{1H} NMR (100 MHz, CDCl3) δ 157.9, 139.0, 137.3,
132.1, 129.6, 129.0, 128.5, 126.5, 125.6, 113.7, 55.3, 55.2,
48.6, 35.7, 29.3, 28.2, 19.0 ppm; GC-MS for C19H23NO, m/z
= 281 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C19H23NOH 282.1852; Found 282.1843.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
C14H15N, m/z = 197 (M+). H and 13C NMR spectral data
were in good agreement with the literature values.36
Bis(4-methylbenzyl)amine (4b). A chlorobenzene (2.0
N-Cyclohexyl-5-methoxytryptamine (3bb). A chloroben-
zene (2.0 mL) solution of complex
mL) solution of complex
1
(13 mg, 0.75 mol %), L1 (16 mg,
1
(13 mg, 0.75 mol %),
10 mol %) and 4-methylbenzylamine (121 mg, 1.0 mmol)
was stirred at 130 °C for 16 h. The product 4b was isolated
by a column chromatography on silica gel (n-hexane/ethyl
acetate = 100:1 to 10:1; 106 mg, 94%). TLC; Rf = 0.4 (20%
EtOAc in hexanes). Data for 4b: 1H NMR (400 MHz, CDCl3)
δ 7.27 (d, J = 7.9 Hz, 4H), 7.18 (d, J = 7.9 Hz, 4H), 3.80 (s,
4H), 2.38 (s, 6H), 1.70 (br s, 1H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 137.2, 136.4, 129.0, 128.1, 52.7, 21.1 ppm;
GC-MS for C16H19N, m/z = 225 (M+). 1H and 13C NMR spec-
tral data were in good agreement with the literature val-
ues.36,37
L1 (16 mg, 10 mol %), 5-methoxytryptamine (190 mg, 1.0
mmol) and cyclohexylamine (139 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3bb was isolated by
a column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 218 mg, 80%). TLC; Rf = 0.2 (30% EtOAc in
1
hexanes). Data for 3bb: H NMR (400 MHz, CDCl3) δ 8.21
(br s, 1H), 7.26–7.20 (m, 1H), 7.08–7.05 (m, 1H), 7.02–6.99
(m, 1H), 6.85 (dd, J = 8.8, 2.5 Hz, 1H), 3.86 (s, 3H), 3.07–
2.90 (m, 4H), 2.45 (tt, J = 10.5, 3.7 Hz, 1H), 1.91–1.78 (m,
3H), 1.75–1.65 (m, 2H), 1.64–1.55 (m, 1H), 1.29–0.99 (m,
5H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 153.8, 131.5,
127.8, 122.8, 113.6, 112.1, 111.8, 100.6, 56.8, 55.9, 46.8,
33.5, 26.1, 25.9, 25.0 ppm; GC-MS for C17H24N2O, m/z =
272 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C17H24FN2OH 273.1961; Found 273.1960.
Bis(4-methoxylbenzyl)amine (4c). A chlorobenzene (2.0
mL) solution of complex
1
(13 mg, 0.75 mol L1 (16 mg, 10
mol %) and 4-methoxylbenzylamine (137 mg, 1.0 mmol)
was stirred at 130 °C for 16 h. The product 4c was isolated
by
a
column chromatography on silica gel (n-
N-Cyclohexyl-2-furanmethanamine (3cc). A chloroben-
zene (2.0 mL) solution of complex
L1 (16 mg, 10 mol %), 2-(2-aminoethyl)furan (97 mg, 1.0
mmol) and cyclohexylamine (139 mg, 1.4 mmol) was
stirred at 130 °C for 16 h. The product 3cc was isolated by
a column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 124 mg, 69%). TLC; Rf = 0.3 (10% EtOAc in
hexane/EtOAc = 100:1 to 10:1; 111 mg, 86%). TLC; Rf =
0.3 (10% EtOAc in hexanes). Data for 4c 1H NMR (400
MHz, CDCl3) δ 7.29–7.24 (m, 4H), 6.91–6.86 (m, 4H), 3.81
(s, 6H), 3.74 (s, 4H), 1.69 (br s, 1H) ppm; 13C{1H} NMR
(100 MHz, CDCl3) δ 158.5, 132.4, 129.2, 113.6, 55.1, 52.3
1
(13 mg, 0.75 mol %),
1
ppm; GC-MS for C16H19NO2, m/z = 257 (M+). H and 13C
NMR spectral data were in good agreement with the litera-
ture values.36,37
1
hexanes). Data for 3cc: H NMR (400 MHz, CDCl3) δ 7.32
(dd, J = 1.9, 0.9 Hz, 1H), 6.28 (dd, J = 3.2, 1.9 Hz, 1H), 6.14–
6.12 (m, 1H), 3.78 (s, 2H), 2.42 (tt, J = 10.4, 3.8, Hz, 1H),
1.90–1.81 (m, 2H), 1.74–1.66 (m, 2H), 1.63–1.46 (m, 2H),
1.28–1.02 (m, 5H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
154.2, 141.5, 110.0, 106.4, 55.7, 43.2, 33.2, 26.0, 24.9 ppm;
GC-MS for C11H17NO, m/z = 179 (M+). H and 13C NMR
spectral data were in good agreement with the literature
N,N-Bis(4-chlorobenzyl)amine (4d). A chlorobenzene
(2.0 mL) solution of complex
1
(13 mg, 0.75 mol %), L1
(16 mg, 10 mol %) and 4-chlorobenzylamine (141 mg, 1.0
mmol) was stirred at 130 °C for 16 h. The product 4d was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 122 mg, 92%). TLC; Rf =
0.5 (10% EtOAc in hexanes). Data for 4d 1H NMR (400
MHz, CDCl3) δ 7.33–7.28 (m, 8H), 3.76 (s, 4H), 1.64 (br s,
1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 138.5, 132.6,
129.4, 128.5, 52.2 ppm; GC-MS for C14H13Cl2N, m/z = 265
1
values.35
4-[2-Cyclohexylaminoethyl]phenol (3dd). A chloroben-
zene (2.0 mL) solution of complex
L1 (16 mg, 10 mol %), tyramine (136 mg, 1.0 mmol) and
cyclohexylamine (139 mg, 1.4 mmol) was stirred at 130 °C
for 16 h. The product 3dd was isolated by a column chro-
matography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 152 mg, 69%). TLC; Rf = 0.3 (20% EtOAc in hexanes).
1
(13 mg, 0.75 mol %),
1
(M+). H and 13C NMR spectral data were in good agree-
ment with the literature values.37,38
N-([1,1'-Biphenyl]-4-ylmethyl)-[1,1'-biphenyl]-4-
methanamine (4e). A chlorobenzene (2.0 mL) solution of
complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol %) and
1
Data for 3dd: H NMR (400 MHz, CDCl3) δ 7.02 (d, J = 8.3
4-phenylbenzylamine (183 mg, 1.0 mmol) was stirred at
130 °C for 16 h. The product 4e was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 148 mg, 85%). TLC; Rf = 0.5 (20% EtOAc in hexanes).
Data for 4e 1H NMR (400 MHz, CDCl3) δ 7.59 (t, J = 8.4 Hz,
8H), 7.49–7.42 (m, 8H), 7.34 (t, J = 7.6 Hz, 2H), 3.90 (s,
Hz, 2H), 6.72 (d, J = 8.3 Hz, 2H), 4.71 (br s, 1H), 2.93 (t, J =
6.9 Hz, 2H), 2.75 (t, J = 6.9 Hz, 2H), 2.47 (tt, J = 10.6, 3.6
Hz, 1H), 1.92–1.85 (m, 2H), 1.75–1.66 (m, 2H), 1.64–1.55
(m, 1H), 1.28–1.08 (m, 5H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 155.5, 130.0, 129.7, 115.9, 56.9, 47.6, 34.7, 32.9,
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The Journal of Organic Chemistry
4H), 1.65 (br s, 1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
yl)methanamine (151 mg, 1.0 mmol) was stirred at 130 °C
1
2
3
4
5
6
7
8
140.9, 139.9, 139.4, 128.7, 128.6, 127.1, 127.0, 52.8 ppm
(one carbon signal obscured or overlapping); GC-MS for
for 16 h. The product 4j was isolated by a column chroma-
tography on silica gel (n-hexanes/EtOAc = 100:1 to 10:1;
110 mg, 77%). TLC; Rf = 0.4 (40% EtOAc in hexanes). Data
1
C26H23N, m/z = 349 (M+). H and 13C NMR spectral data
were in good agreement with the literature values.39
4j
for 1H NMR (400 MHz, CDCl3) δ 6.85 (s, 2H), 6.77–6.75
(m, 4H), 5.94 (s, 4H), 3.69 (s, 4H), 1.59 (br s, 1H) ppm;
13C{1H} NMR (100 MHz, CDCl3) δ 147.7, 146.5, 134.3,
121.2, 108.7, 108.0, 100.9, 52.7 ppm; GC-MS for C16H15NO4,
m/z = 285 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C16H15NO4H 286.1074; Found 286.1070.
4-Fluoro-N-[(4-
fluorophenyl)methyl]benzenemethanamine (4f). A chloro-
benzene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol
%), L1 (16 mg, 10 mol %) and 4-phenylbenzylamine (125
mg, 1.0 mmol) was stirred at 130 °C for 16 h. The product
4f was isolated by a column chromatography on silica gel
(n-hexanes/EtOAc = 100:1 to 10:1; 106 mg, 91%). TLC; Rf
= 0.4 (20% EtOAc in hexanes). Data for 4f 1H NMR (400
MHz, CDCl3) δ 7.36–7.28 (m, 4H), 7.07–6.99 (m, 4H), 3.78
(s, 4H), 1.67 (br s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
161.8 (d, JCF = 244.5 Hz), 135.8 (d, JCF = 3.1 Hz), 129.6 (d,
JCF = 8.0 Hz), 115.1 (d, JCF = 21.3 Hz), 52.3 ppm; GC-MS for
9
Bis(3,4,5-trimethoxylbenzyl)amine (4k). A chloroben-
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
zene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol %),
L1 (16 mg, 10 mol %) and 3,4,5-trimethoxylbenzylamine
(197 mg, 1.0 mmol) was stirred at 130 °C for 16 h. The
product 4k was isolated by a column chromatography on
silica gel (n-hexane/EtOAc = 100:1 to 10:1; 115 mg, 61%).
TLC; Rf = 0.3 (50% EtOAc in hexanes). Data for 4k 1H NMR
(400 MHz, CDCl3) 6.56 (s, 4H), 3.84 (s, 12H), 3.81 (s, 6H),
3.74 (s, 4H), 1.80 (br s, 1H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 153.1, 136.6, 135.8, 104.7, 60.7, 55.9, 53.3 ppm;
GC-MS for C20H27NO6, m/z = 377 (M+); HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C20H27NO6H 378.1911; Found
378.1892.
1
C14H13F2N, m/z = 233 (M+). H and 13C NMR spectral data
were in good agreement with the literature values.38
4-(Trifluoromethyl)-N-[[4-
(trifluoromethyl)phenyl]methyl]benzenemethanamine
(4g). A chlorobenzene (2.0 mL) solution of complex
1
(13
mg, 0.75 mol %), L1 (16 mg, 10 mol %) and 4-
(trifluoromethyl)benzenemethanamine (175 mg, 1.0
mmol) was stirred at 130 °C for 16 h. The product 4g was
isolated by a column chromatography on silica gel (n-
hexanes/EtOAc = 100:1 to 10:1; 140 mg, 84%). TLC; Rf =
0.5 (20% EtOAc in hexanes). Data for 4g 1H NMR (400
MHz, CDCl3) δ 7.64–7.57 (m, 4H), 7.51–7.46 (m, 4H), 3.88
(s, 4H), 1.75 (br s, 1H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 144.1, 129.4 (q, JCF = 32.4 Hz), 128.3, 125.3 (q, JCF
= 3.8 Hz), 124.2 (q, JCF = 271.8 Hz), 52.6 ppm; GC-MS for
4-Methoxy-N-[(1R)-1-(4-methoxyphenyl)ethyl]-α-
methyl-(αR)-benzenemethanamine (4l). A chlorobenzene
(2.0 mL) solution of complex
1
(13 mg, 0.75 mol %), L1
(16 mg, 10 mol
%)
and (R)-(+)-1-(4-
methoxyphenyl)ethylamine (151 mg, 1.0 mmol) was
stirred at 130 °C for 16 h. The product 4l was isolated by a
column chromatography on silica gel (n-hexanes/EtOAc =
100:1 to 10:1; 107 mg, 75%), 7:1 mixture of diastere-
omers, [a]ꢁꢀꢁ = -211.1 (c = 0.12 in CH2Cl2); TLC; Rf = 0.3
(20% EtOAc in hexanes). Data for 4l 1H NMR (400 MHz,
CDCl3) δ 7.13 (d, J = 8.6 Hz, 4H), 6.89–6.84 (m, 4H), 3.82
(s, 6H), 3.45 (q, J = 6.7 Hz, 2H), 1.54 (br s, 1H), 1.25 (d, J =
6.7 Hz, 6H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 158.4,
137.7, 127.6, 113.7, 55.2, 54.2, 24.9 ppm; GC-MS for
C18H23NO2, m/z = 285 (M+). 1H and 13C NMR spectral data
were in good agreement with the literature values.42
1
C16H13F6N, m/z = 333 (M+). H and 13C NMR spectral data
were in good agreement with the literature values.38,40
Bis(3-methoxylbenzyl)amine (4h). A chlorobenzene (2.0
mL) solution of complex
1
(13 mg, 0.75 mol %), L1 (16 mg,
10 mol %) and 3-methoxylbenzylamine (137 mg, 1.0
mmol) was stirred at 130 °C for 16 h. The product 4h was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 108 mg, 84%). TLC; Rf =
0.3 (10% EtOAc in hexanes). Data for 4h 1H NMR (400
MHz, CDCl3) δ 7.29–7.22 (m, 2H), 6.97–6.91 (m, 4H), 6.84–
6.78 (m, 2H), 3.82 (s, 6H), 3.80 (s, 4H), 1.71 (br s, 1H)
ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 159.6, 141.9, 129.3,
120.4, 113.5, 112.4, 55.1, 53.0 ppm; GC-MS for C16H19NO2,
4-Methoxy-N-[2-(4-
methoxyphenyl)ethyl]benzeneethanamine (4m). A chloro-
benzene (2.0 mL) solution of complex (13 mg, 0.75 mol
%), (16 mg, 10 mol %) and 4-
L1
methoxybenzeneethanamine (151 mg, 1.0 mmol) was
4m
1
stirred at 130 °C for 16 h. The product
was isolated by
1
m/z = 257 (M+). H and 13C NMR spectral data were in
a column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 127 mg, 89%). TLC; Rf = 0.3 (10% EtOAc in
hexanes). Data for 4m 1H NMR (400 MHz, CDCl3) δ 7.10–
7.05 (m, 4H), 6.84–6.79 (m, 4H), 3.79 (s, 6H), 2.88–2.82
(m, 4H), 2.76–2.70 (m, 4H), 1.56 (br s, 1H) ppm; 13C{1H}
NMR (100 MHz, CDCl3) δ 157.9, 131.9, 129.5, 113.8, 55.2,
51.2, 35.3 ppm; GC-MS for C18H23NO2, m/z = 285 (M+);
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C18H23NO2H
286.1802; Found 286.1800.
good agreement with the literature values.36
N,N-Bis(3-chlorobenzyl)amine (4i). A chlorobenzene
(2.0 mL) solution of complex
1
(13 mg, 0.75 mol %), L1
(16 mg, 10 mol %) and 3-chlorobenzylamine (141 mg, 1.0
mmol) was stirred at 130 °C for 16 h. The product 4i was
isolated by a column chromatography on silica gel (n-
hexanes/EtOAc = 100:1 to 10:1; 118 mg, 89%). TLC; Rf =
0.3 (10% EtOAc in hexanes). Data for 4i 1H NMR (400 MHz,
CDCl3) δ 7.37–7.34 (m, 2H), 7.29–7.19 (m, 6H), 3.77 (s,
4H), 1.65 (br s, 1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
142.1, 134.2, 129.6, 128.1, 127.2, 126.2, 52.5 ppm; GC-MS
3-Methoxy-N-[2-(3-
methoxyphenyl)ethyl]benzeneethanamine (4n).
A chloro-
(13 mg, 0.75 mol
%) and 3-
benzene (2.0 mL) solution of complex
L1
1
1
for C14H13Cl2N, m/z = 265 (M+). H and 13C NMR spectral
%),
(16
mg,
10
mol
data were in good agreement with the literature values.41
methoxybenzeneethanamine (139 mg, 1.0 mmol) was
stirred at 130 °C for 16 h. The product 4n was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1). Isolated yield: 128 mg, 90%. TLC; Rf = 0.3
Bis(3,4-methylenedioxybenzyl)amine (4j). A chloroben-
zene (2.0 mL) solution of complex (13 mg, 0.75 mol %),
1
L1 (16 mg, 10 mol %) and 1-(1,3-benzodioxol-5-
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(10% EtOAc in hexanes). Data for 4n 1H NMR (400 MHz, Data for 4r 1H NMR (400 MHz, CDCl3) δ 7.30–7.24 (m, 4H),
1
2
3
4
5
6
7
8
CDCl3) δ 7.23–7.16 (m, 2H), 6.80–6.71 (m, 6H), 3.79 (s,
6H), 2.91 (t, J = 7.2 Hz, 4H), 2.79 (t, J = 7.2 Hz, 4H), 1.91
(br s, 1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 159.6,
141.4, 129.4, 121.0, 114.3, 111.5, 55.1, 50.9, 36.2 ppm; GC-
MS for C18H23NO2, m/z = 285 (M+); HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C18H23NO2H 286.1802; Found 286.1798.
7.24–7.18 (m, 4H), 3.83 (quintet, J = 7.2 Hz, 2H), 3.26 (dd,
J = 15.4, 7.2 Hz, 4H), 2.85 (dd, J = 15.4, 7.2 Hz, 4H), 1.77
(br s, 1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 141.5,
126.3, 124.5, 58.1, 40.2 ppm; GC-MS for C18H19N, m/z =
249 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C18H19NH 250.1590; Found 250.1598.
3-Fluoro-N-[2-(3-
Bis(cyclohexyl)amine (4s). A chlorobenzene (2.0 mL)
fluorophenyl)ethyl]benzeneethanamine (4o). A chloro-
solution of complex (13 mg, 0.75 mol %), L1 (16 mg, 10
1
benzene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol
mol %) and cyclohexylamine (99 mg, 1.0 mmol) was
stirred at 130 °C for 16 h. The product 4s was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
100:1 to 10:1; 86 mg, 95%). TLC; Rf = 0.3 (20% EtOAc in
hexanes). Data for 4s 1H NMR (400 MHz, CDCl3) δ 2.47 (tt, J
= 10.6, 3.7 Hz, 2H), 1.82–1.74 (m, 4H), 1.68–1.59 (m, 4H),
1.57–1.49 (m, 2H), 1.24–0.88 (m, 10H) ppm; 13C{1H} NMR
(100 MHz, CDCl3) δ 52.8, 34.1, 26.0, 25.1 ppm; GC-MS for
9
%), L1 (16 mg, 10 mol %) and 3-fluorobenzeneethanamine
(139 mg, 1.0 mmol) was stirred at 130 °C for 16 h. The
product 4o was isolated by a column chromatography on
silica gel (n-hexane/EtOAc = 100:1 to 10:1; 114 mg, 87%).
TLC; Rf = 0.4 (10% EtOAc in hexanes). Data for 4o 1H NMR
(400 MHz, CDCl3) δ 7.26–7.18 (m, 2H), 6.98–6.83 (m, 6H),
2.93–2.86 (m, 4H), 2.82–2.76 (m, 4H), 1.68 (br s, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 162.9 (d, JCF = 245.7 Hz),
142.3 (d, JCF = 7.1 Hz), 129.9 (d, JCF = 8.3 Hz), 124.3 (d, JCF
= 2.8 Hz), 115.4 (d, JCF = 20.9 Hz), 113.1 (d, JCF = 21.0 Hz),
50.6, 35.9 (d, JCF = 1.4 Hz) ppm; GC-MS for C16H17F2N, m/z
= 261 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C16H17F2NH 262.1402; Found 262.1389.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
C12H23N, m/z = 181 (M+). H and 13C NMR spectral data
were in good agreement with the literature values.45,46
N-(2-Thienylethyl)-2-thiopheneethanamine (4t). A chlo-
robenzene (2.0 mL) solution of complex
1
(13 mg, 0.75
mol %), L1 (16 mg, 10 mol %) and 2-thiopheneethanamine
(127 mg, 1.0 mmol) was stirred at 130 °C for 16 h. The
product 4t was isolated by a column chromatography on
silica gel (n-hexane/EtOAc = 100:1 to 10:1; 106 mg, 89%).
TLC; Rf = 0.4 (30% EtOAc in hexanes). Data for 4t 1H NMR
(400 MHz, CDCl3) δ 7.22–7.04 (m, 2H), 6.96–6.87 (m, 2H),
6.85–6.75 (m, 2H), 3.06–2.99 (m, 4H), 2.98–2.90 (m, 4H),
2.45 (br s, 1H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
142.2, 126.8, 125.0, 123.5, 50.7, 30.2 ppm; GC-MS for
C12H15NS2, m/z = 237 (M+); HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C12H15NS2H 238.0719; Found 238.0716.
β-Methyl-N-(2-phenylpropyl)benzeneethanamine (4p).
A chlorobenzene (2.0 mL) solution of complex
1
(13 mg,
0.75 mol %), L1 (16 mg, 10 mol %) and (R)-(+)-β-
methylphenethylamine (135 mg, 1.0 mmol) was stirred at
130 °C for 16 h. The product 4p was isolated by a column
chromatography on silica gel (n-hexane/ethyl acetate =
100:1 to 10:1; 118 mg, 93%), 1.15:1 mixture of diastere-
omers. TLC; Rf = 0.5 (30% EtOAc in hexanes). Data for 4p
1H NMR (400 MHz, CDCl3) δ 7.26–7.21 (m, 4H), 7.20–7.14
(m, 2H), 7.13–7.07 (m, 4H), 2.95–2.84 (m, 2H), 2.84–2.66
(m, 4H), 1.49 (br s, 1H), 1.21–1.17 (2d, J = 6.9 Hz, 6H)
ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 145.1, 128.5, 127.0,
126.2, 56.7, 39.5, 19.8 ppm; GC-MS for C18H23N, m/z = 253
Di-n-hexylamine (4u). A chlorobenzene (2.0 mL) solu-
tion of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol
%) and 1-hexamine (101 mg, 1.0 mmol) was stirred at 130
°C for 16 h. The product 4u was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 40 mg, 43%). TLC; Rf = 0.3 (30% EtOAc in hexanes).
1
(M+). H and 13C NMR spectral data were in good agree-
ment with the literature values.43
1
α-Methyl-N-(1-methyl-3-
Data for 4u: H NMR (400 MHz, CDCl3) δ 2.59 (t, J = 7.4,
phenylpropyl)benzenepropanamine (4q). A chloroben-
4H), 2.24 (br s, 1H), 1.54–1.44 (m, 4H), 1.35–1.19 (m,
12H), 0.90–0.82 (m, 6H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 50.0, 31.7, 29.8, 27.1, 22.6, 14.0 ppm; GC-MS for
zene (2.0 mL) solution of complex
1
(13 mg, 0.75 mol %),
L1 (16 mg, 10 mol %) and α-methylbenzenepropanamine
(149 mg, 1.0 mmol) was stirred at 130 °C for 16 h. The
product 4p was isolated by a column chromatography on
silica gel (n-hexane/EtOAc = 100:1 to 10:1; 126 mg, 90%),
1:1 mixture of diastereomers. TLC; Rf = 0.5 (40% EtOAc in
hexanes). Data for 4q 1H NMR (400 MHz, CDCl3) δ 7.58–
6.97 (m, 10H), 2.85–2.74 (m, 2H), 2.73–2.58 (m, 4H), 1.84–
1.70 (m, 2H), 1.69–1.57 (m, 2H), 1.15–1.04 (m, 6H) ppm;
13C{1H} NMR (100 MHz, CDCl3) δ 142.4 (isomers 1 and 2),
128.3 (isomers 1 and 2), 128.2 (isomers 1 and 2), 125.6
(isomers 1 and 2), 49.4 (isomer 1), 49.2 (isomer 2), 39.3
(isomer 1), 38.8 (isomer 2), 32.4 (isomer 1), 32.2 (isomer
2), 21.1 (isomer 1), 20.7 (isomer 2) ppm; GC-MS for
1
C12H27N, m/z = 185 (M+). H and 13C NMR spectral data
were in good agreement with the literature values.46,47
N,N-Dibutylamine (4v). A chlorobenzene (2.0 mL) solu-
tion of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10 mol
%) and n-butylamine (73 mg, 1.0 mmol) was stirred at 130
°C for 16 h. The product 4v was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 30 mg, 46%). TLC; Rf = 0.3 (30% EtOAc in hexanes).
Data for 4v: 1H NMR (400 MHz, CDCl3) δ 2.43 (t, J = 7.2 Hz,
4H), 1.37–1.25 (m, 4H), 1.24–1.11 (m, 4H), 0.86 (br s, 1H),
0.75 (t, J = 7.3 Hz, 6H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 49.6, 32.1, 20.2, 13.7 ppm; GC-MS for C8H19N, m/z
1
C20H27N, m/z = 281 (M+). H and 13C NMR spectral data
1
= 129 (M+). H and 13C NMR spectral data were in good
were in good agreement with the literature values.44
agreement with the literature values.47
Di-[2-aminoindane] (4r). A chlorobenzene (2.0 mL) so-
N-(2-Furanylmethyl)-2-furanmethanamine (4w).
A
lution of complex
1
(13 mg, 0.75 mol %), L1 (16 mg, 10
chlorobenzene (2.0 mL) solution of complex (13 mg, 0.75
1
mol %) and 2-indanamine (133 mg, 1.0 mmol) was stirred
at 130 °C for 16 h. The product 4r was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 100:1 to
10:1; 91 mg, 73%). TLC; Rf = 0.5 (20% EtOAc in hexanes).
mol %), L1 (16 mg, 10 mol %) and Furfurylamine (97 mg,
1.0 mmol) was stirred at 130 °C for 16 h. The product 4w
was isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 100:1 to 10:1; 70 mg, 79%). TLC; Rf = 0.3
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The Journal of Organic Chemistry
1
(30% EtOAc in hexanes). Data for 4w: H NMR (400 MHz,
CDCl3) δ 7.40–7.31 (m, 2H), 6.34–6.27 (m, 2H), 6.22–6.13
(m, 2H), 3.78 (s, 4H), 1.89 (br s, 1H) ppm; 13C{1H} NMR
(100 MHz, CDCl3) δ 153.3, 141.9, 110.1, 107.2, 44.9 ppm;
spectral data were in good agreement with the literature
values.53
1
2
3
4
5
6
7
8
4-Fluoro-N-(4-methoxyphenyl)benzenemethanamine
(5d). A chlorobenzene (2.0 mL) solution of complex
1
(7
GC-MS for C10H11NO2, m/z = 177 (M+). H and 13C NMR
spectral data were in good agreement with the literature
1
mg, 0.75 mol %), L1 (8 mg, 10 mol %), 4-methoxyaniline
(62 mg, 0.5 mmol) and 4-fluorobenzylamine (88 mg, 0.7
mmol) was stirred at 140 °C for 20 h. The product 5d was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 150:1 to 40:1; 47 mg, 41%). TLC; Rf = 0.3
values.48
N-(3-Phenylpropyl)benzenepropanamine (4x). A chlo-
robenzene (2.0 mL) solution of complex
mol %), L1 (16 mg, 10 mol %) and 3-phenyl-1-
propanamine (135 mg, 1.0 mmol) was stirred at 130 °C for
16 h. The product 4x was isolated by a column chromatog-
raphy on silica gel (n-hexane/EtOAc = 100:1 to 10:1; 53
mg, 42%). TLC; Rf = 0.3 (30% EtOAc in hexanes). Data for
1
(13 mg, 0.75
1
(20% EtOAc in hexanes). Data for 5d: H NMR (400 MHz,
9
CDCl3) δ 7.38–7.30 (m, 2H), 7.07–6.99 (m, 2H), 6.83–6.76
(m, 2H), 6.66–6.59 (m, 2H), 4.26 (s, 2H), 4.09 (br s, 1H),
3.75 (s, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 162.0
(d, JCF = 245.1 Hz), 152.4, 141.7, 135.0 (d, JCF = 3.1 Hz),
129.1 (d, JCF = 8.0 Hz), 115.3 (d, JCF = 21.4 Hz), 114.8,
114.4, 55.7, 48.6 ppm; GC-MS for C14H14FNO m/z = 231
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
4x: H NMR (400 MHz, CDCl3) δ 7.34–7.14 (m, 10H), 2.65
(t, J = 7.4 Hz, 8H), 1.89 (brs, 1H), 1.84 (quintet, J = 7.4 Hz,
4H); 13C{1H} NMR (100 MHz, CDCl3) δ 142.0, 128.3, 128.3,
125.8, 49.4, 33.6, 31.5 ppm; GC-MS for C18H23N, m/z = 253
(M+). H and 13C NMR spectral data were in good agree-
1
(M+). H and 13C NMR spectral data were in good agree-
ment with the literature values.54,55
1
N-(4-Chlorophenyl)-4-methoxybenzenemethanamine
ment with the literature values.41
(5e). A chlorobenzene (2.0 mL) solution of complex
1
(7
4-Methoxy-N-phenylbenzenemethanamine (5a). A chlo-
mg, 0.75 mol %), L1 (8 mg, 10 mol %), 4-chloroaniline (64
mg, 0.5 mmol) and 4-methoxybenzylamine (96 mg, 0.7
mmol) was stirred at 140 °C for 20 h. The product 5e was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 150:1 to 40:1; 73 mg, 59%). TLC; Rf = 0.5
robenzene (2.0 mL) solution of complex
1
(7 mg, 0.75 mol
%), L1 (8 mg, 10 mol %), aniline (47 mg, 0.5 mmol) and 4-
methoxybenzylamine (96 mg, 0.7 mmol) was stirred at
140 °C for 20 h. The product 5a was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 150:1 to
40:1; 76 mg, 71%). TLC; Rf = 0.4 (30% EtOAc in hexanes).
Data for 5a: 1H NMR (400 MHz, CDCl3) δ 7.29 (d, J = 8.6 Hz,
2H), 7.22–7.16 (m, 2H), 6.88 (d, J = 8.6 Hz, 2H), 6.77–6.72
(m, 1H), 6.70–6.65 (m, 2H), 4.26 (s, 2H), 3.80 (s, 3H) ppm;
13C{1H} NMR (100 MHz, CDCl3) δ 158.9, 147.1, 130.6,
129.3, 129.1, 118.4, 114.0, 113.6, 55.3, 48.4 ppm; GC-MS
1
(20% EtOAc in hexanes). Data for 5e: H NMR (400 MHz,
CDCl3) 7.30–7.25 (m, 2H), 7.14–7.09 (m, 2H), 6.92–6.87
(m, 2H), 6.59–6.53 (m, 2H), 4.23 (s, 2H), 4.15 (br s, 1H),
3.81 (s, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 158.9,
146.5, 130.7, 129.0, 128.7, 122.1, 114.0, 114.0, 55.3, 47.9
1
ppm; GC-MS for C14H14ClNO, m/z = 247 (M+). H and 13C
NMR spectral data were in good agreement with the litera-
ture values.56
1
for C14H15NO, m/z = 213 (M+). H and 13C NMR spectral
data were in good agreement with the literature values.49,50
3,4,5-Trimethoxy-N-(4-
methoxyphenyl)benzenemethanamine (5f). A chloroben-
1
zene (2.0 mL) solution of complex (7 mg, 0.75 mol %), L1
N-(4-Methoxyphenyl)phenylmethanamine (5b). A chlo-
robenzene (2.0 mL) solution of complex
1
(7 mg, 0.75 mol
%), L1 (8 mg, 10 mol %), 4-methoxyaniline (62 mg, 0.5
mmol) and benzylamine (75 mg, 0.7 mmol) was stirred at
140 °C for 20 h. The product 5b was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 150:1 to
40:1; 61 mg, 57%). TLC; Rf = 0.3 (20% EtOAc in hexanes).
Data for 5b: 1HNMR (400 MHz, CDCl3) δ 7.46–7.29 (m, 5H),
6.87–6.81 (m, 2H), 6.69–6.63 (m, 2H), 4.33 (s, 2H), 3.79 (s,
3H), ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 152.1, 142.2,
139.5, 128.5, 127.5, 127.1, 114.8, 114.1, 55.7, 49.1 ppm;
(8 mg, 10 mol %), 4-methoxyaniline (62 mg, 0.5 mmol)
and 3,4,5-trimethoxybenzylamine (138 mg, 0.7 mmol) was
stirred at 140 °C for 20 h. The product 5f was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
150:1 to 40:1; 138 mg, 91%). TLC; Rf = 0.5 (50% EtOAc in
1
hexanes). Data for 5f: H NMR (400 MHz, CDCl3) δ 6.81–
6.76 (m, 2H), 6.65–6.60 (m, 4H), 4.21 (s, 2H), 3.84 (s, 9H),
3.74 (s, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 153.3,
152.3, 142.1, 136.9, 135.3, 114.8, 114.3, 104.3, 60.8, 56.0,
1
1
GC-MS for C14H15NO, m/z = 213 (M+). H and 13C NMR
55.7, 49.7 ppm; GC-MS for C17H21NO4, m/z = 303 (M+). H
spectral data were in good agreement with the literature
values.51,52
and 13C NMR spectral data were in good agreement with
the literature values.57,58
N-(4-Methoxyphenyl)[1,1'-biphenyl]-4-methanamine
3,4,5-Trimethoxy-N-phenylbenzenemethanamine (5g).
1
A chlorobenzene (2.0 mL) solution of complex (7 mg,
(5c). A chlorobenzene (2.0 mL) solution of complex
1
(7
mg, 0.75 mol %), L1 (8 mg, 10 mol %), 4-methoxyaniline
(62 mg, 0.5 mmol) and 4-phenylbenzylamine (128 mg, 0.7
mmol) was stirred at 140 °C for 20 h. The product 5c was
isolated by a column chromatography on silica gel (n-
hexane/ethyl acetate = 150:1 to 40:1; 101 mg, 70%). TLC;
Rf = 0.4 (30% EtOAc in hexanes). Data for 5c: 1H NMR (400
MHz, CDCl3) δ 7.61–7.55 (m, 4H), 7.47–7.42 (m, 4H), 7.35
(tt, J = 7.3, 1.3, Hz, 1H), 6.82–6.77 (m, 2H), 6.69–6.65 (m,
2H), 4.34 (s, 2H), 3.75 (s, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 152.5, 141.7, 140.8, 140.2, 138.3, 128.7,
128.1, 127.3, 127.2, 127.0, 114.9, 114.6, 55.8, 49.2 ppm;
GC-MS for C20H19NO m/z = 289 (M+). 1H and 13C NMR
0.75 mol %), L1 (8 mg, 10 mol %), aniline (47 mg, 0.5
mmol) and 3,4,5-trimethoxybenzylamine (138 mg, 0.7
mmol) was stirred at 140 °C for 20 h. The product 5g was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 150:1 to 40:1; 97 mg, 71%). TLC; Rf = 0.6
1
(50% EtOAc in hexanes). Data for 5g: H NMR (400 MHz,
CDCl3) δ 7.23–7.17 (m, 2H), 6.75 (tt, J = 7.3, 1.1 Hz, 1H),
6.69–6.65 (m, 2H), 6.63 (s, 2H), 4.27 (s, 2H), 4.13 (br s,
1H), 3.86 (s, 3H), 3.85 (s, 6H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 153.3, 148.0, 136.8, 135.1, 129.1, 117.6,
112.8, 104.2, 60.7, 55.9, 48.7 ppm; GC-MS for C16H19NO3,
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The Journal of Organic Chemistry
Page 14 of 18
1
m/z = 273 (M+). H and 13C NMR spectral data were in
MS for C16H17NO, m/z = 239 (M+); HRMS (ESI-TOF) m/z:
good agreement with the literature values.59,60
[M+H]+ Calcd for C16H17NOH 240.1383; Found 240.1377.
1
2
3
4
5
6
7
8
9
3,4,5-Trimethoxy-N-(4-
chlorophenyl)benzenemethanamine (5h). A chloroben-
zene (2.0 mL) solution of complex
4-(2-(3,4,5-Trimethoxyphenylamino)ethyl)phenol (5l).
1
A chlorobenzene (2.0 mL) solution of complex (7 mg,
1
(7 mg, 0.75 mol %), L1
0.75 mol %), L1 (8 mg, 10 mol %), 3,4,5-trimethoxyaniline
(91 mg, 0.5 mmol) and 2-(4-hydroxyphenyl)ethanamine
(96 mg, 0.7 mmol) was stirred at 140 °C for 20 h. The
product 5l was isolated by a column chromatography on
silica gel (n-hexane/EtOAc = 150:1 to 40:1; 77 mg, 51%).
TLC; Rf = 0.4 (50% EtOAc in hexanes). Data for 5l: 1H NMR
(400 MHz, CDCl3) δ 7.09–7.05 (m, 2H), 6.81–6.77 (m, 2H),
5.90 (s, 2H), 3.81 (s, 6H), 3.77 (s, 3H), 3.33 (t, J = 7.1 Hz,
2H), 2.86 (t, J = 7.1 Hz, 2H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 154.4, 153.9, 144.1, 130.7, 130.5, 129.8, 115.5,
91.1, 61.1, 55.9, 46.2, 34.4 ppm; GC-MS for C17H21NO4, m/z
= 303 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C17H21NO4H 304.1543; Found 304.1516.
(8 mg, 10 mol %), 4-chloroaniline (64 mg, 0.5 mmol) and
3,4,5-trimethoxybenzylamine (138 mg, 0.7 mmol) was
stirred at 140 °C for 20 h. The product 5h was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
150:1 to 40:1; 111 mg, 72%). TLC; Rf = 0.6 (50% EtOAc in
hexanes). Data for 5h: 1H NMR (400 MHz, CDCl3) δ 7.12 (d,
J = 9.0 Hz, 2H), 6.58 (s, 2H), 6.57 (d, J = 9.0 Hz, 2H), 4.23
(s, 2H), 3.84 (s, 3H), 3.84 (s, 6H) ppm; 13C{1H} NMR (100
MHz, CDCl3) δ 153.4, 146.4, 137.0, 134.5, 129.0, 122.3,
114.0, 104.1, 60.8, 56.0, 48.8 ppm; GC-MS for C16H18ClNO3,
m/z = 307 (M+). Anal. Calcd for C16H18ClNO3: C, 62.44; H,
5.90. Found: C, 62.88; H, 6.05.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N-Hexyl-4-methoxybenzenamine (5i). A chlorobenzene
(2.0 mL) solution of complex
N-(3,4,5-Trimethoxybenzyl)-3,4-dihydro-2H-
1
(7 mg, 0.75 mol %), L1 (8
benzo[b][1,4]dioxepin-7-amine (5m).
(2.0 mL) solution of complex (7 mg, 0.75 mol %), L1 (8
mg, 10 mol %), 3,4-dihydro-2H-1,5-benzodioxepin-7-
amine (83 mg, 0.5 mmol) and 3,4,5-
A chlorobenzene
mg, 10 mol %), 4-methoxyaniline (62 mg, 0.5 mmol) and
1-hexamine (71 mg, 0.7 mmol) was stirred at 140 °C for 20
h. The product 5i was isolated by a column chromatog-
raphy on silica gel (n-hexane/EtOAc = 150:1 to 40:1; 65
mg, 63%). TLC; Rf = 0.4 (20% EtOAc in hexanes). Data for
1
trimethoxybenzylamine (138 mg, 0.7 mmol) was stirred at
140 °C for 20 h. The product 5m was isolated by a column
chromatography on silica gel (n-hexane/EtOAc = 150:1 to
40:1; 129 mg, 75%). TLC; Rf = 0.4 (50% EtOAc in hexanes).
1
5i: H NMR (400 MHz, CDCl3) δ 6.82–6.77 (m, 2H), 6.63–
6.58 (m, 2H), 3.75 (s, 3H), 3.39 (br s, 1H), 3.06 (t, J = 7.2
Hz, 2H), 1.61 (quintet, J = 7.4 Hz, 2H), 1.44–1.26 (m, 6H),
0.91 (t, J = 6.9 Hz, 3H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 152.1, 142.5, 114.8, 114.2, 55.8, 45.2, 31.6, 29.5,
26.8, 22.6, 14.0 ppm; GC-MS for C13H21NO, m/z = 207 (M+).
1H and 13C NMR spectral data were in good agreement with
the literature values.58
1
Data for 5m: H NMR (400 MHz, CDCl3) δ 6.84 (d, J = 8.6
Hz, 1H), 6.59 (s, 2H), 6.38–6.34 (m, 1H), 6.31–6.26 (m,
1H), 4.19 (s, 2H), 4.15 (t, J = 5.4 Hz, 2H), 4.09 (t, J = 5.5 Hz,
2H), 3.84 (s, 6H), 3.83 (s, 3H), 2.14 (quintet, J = 5.5 Hz, 2H)
ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 153.3, 152.1, 143.9,
143.6, 137.0, 134.4, 122.2, 108.7, 106.5, 104.5, 70.9, 70.8,
60.8, 56.1, 49.8, 32.4 ppm; GC-MS for C19H23NO5, m/z =
345 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C19H23FNO5H 346.1649; Found 346.1618.
N-(4-Methoxyphenyl)benzenepropanamine (5j). A chlo-
robenzene (2.0 mL) solution of complex
%), L1 (8 mg, 10 mol %), 4-methoxyaniline (62 mg, 0.5
mmol) and 3-phenyl-1-propanamine (95 mg, 0.7 mmol)
was stirred at 140 °C for 20 h. The product 5j was isolated
1
(7 mg, 0.75 mol
N-(3,5-Dimethoxybenzyl)-4-methoxybenzenamine (5n).
A chlorobenzene (2.0 mL) solution of complex
1
(7 mg,
by
a
column chromatography on silica gel (n-
0.75 mol %), L1 (8 mg, 10 mol %), 4-methoxyaniline (62
mg, 0.5 mmol) and 3,5-dimethoxybenzylamine (117 mg,
0.7 mmol) was stirred at 140 °C for 20 h. The product 5n
was isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 150:1 to 40:1; 115 mg, 84%). TLC; Rf =
hexane/EtOAc = 150:1 to 40:1; 54 mg, 45%). TLC; Rf = 0.9
(50% EtOAc in hexanes). Data for 5j: H NMR (400 MHz,
1
CDCl3) δ 7.34–7.29 (m, 2H), 7.25–7.18 (m, 3H), 6.80 (d, J =
8.9 Hz, 2H), 6.60 (d, J = 8.9 Hz, 2H), 3.76 (s, 3H), 3.13 (t, J
= 7.1 Hz, 2H), 2.75 (t, J = 7.6 Hz, 2H), 1.96 (quintet, J = 7.4
Hz, 2H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 152.2,
142.2, 141.7, 128.4, 128.4, 125.9, 114.8, 114.3, 55.8, 44.6,
33.4, 31.0 ppm; GC-MS for C16H19NO, m/z = 241 (M+). H
and 13C NMR spectral data were in good agreement with
the literature values.61,62
1
0.7 (50% EtOAc in hexanes). Data for 5n: δ H NMR (400
MHz, CDCl3) 6.82–6.77 (m, 2H), 6.64–6.59 (m, 2H), 6.57 (d,
J = 2.3 Hz, 2H), 6.40 (t, J = 2.3 Hz, 1H), 4.23 (s, 2H), 3.79 (s,
6H), 3.76 (s, 3H), ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
160.9, 152.0, 142.3, 142.2, 114.7, 114.0, 105.2, 98.9, 55.6,
1
1
55.2, 49.2 ppm; GC-MS for C16H19NO3, m/z = 273 (M+). H
and 13C NMR spectral data were in good agreement with
the literature values.63
N-(4-Methoxyphenyl)-2,3-dihydro-1H-inden-2-amine
(5k). A chlorobenzene (2.0 mL) solution of complex
1
(7
mg, 0.75 mol %), L1 (8 mg, 10 mol %), 3,4,5-
trimethoxyaniline (62 mg, 0.5 mmol) and 2-aminoindan
(93 mg, 0.7 mmol) was stirred at 140 °C for 20 h. The
product 5k was isolated by a column chromatography on
silica gel (n-hexane/EtOAc = 150:1 to 40:1; 88 mg, 74%).
TLC; Rf = 0.5 (30% EtOAc in hexanes). Data for 5k: 1H NMR
(400 MHz, CDCl3) δ 7.29–7.17 (m, 4H), 6.86–6.80 (m, 2H),
6.67–6.62 (m, 2H), 4.33 (tt, J = 6.8, 4.4 Hz,1H), 3.79 (s, 3H),
3.37 (dd, J = 16.0, 6.8 Hz, 2H), 2.90 (dd, J = 16.0, 4.4 Hz,
2H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 152.2, 141.4,
141.4, 126.5, 124.9, 114.9, 114.9, 55.7, 54.9, 40.1 ppm; GC-
4-Chloro-N-(3,5-dimethoxybenzyl)benzenamine (5o).
A
chlorobenzene (2.0 mL) solution of complex (7 mg, 0.75
1
mol %), L1 (8 mg, 10 mol %), 4-chloroaniline (64 mg, 0.5
mmol) and 3,5-dimethoxybenzylamine (117 mg, 0.7
mmol) was stirred at 140 °C for 20 h. The product 5o was
isolated by a column chromatography on silica gel (n-
hexane/EtOAc = 150:1 to 40:1; 66 mg, 48%). TLC; Rf = 0.6
1
(30% EtOAc in hexanes). Data for 5o: H NMR (400 MHz,
CDCl3) δ 7.13–7.08 (m, 2H), 6.58–6.53 (m, 2H), 6.52–6.49
(m, 2H), 6.38 (t, J = 2.2 Hz, 1H), 4.24 (s, 2H), 3.78 (s, 6H)
ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 161.1, 146.3, 141.3,
129.0, 122.3, 114.1, 105.2, 99.1, 55.3, 48.6 ppm; GC-MS for
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Page 15 of 18
The Journal of Organic Chemistry
C15H16ClNO2, m/z = 277 (M+); HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C15H16NO2ClH 278.0942; Found
278.0928.
mol %), L1 (8 mg, 10 mol %), L-glutamine (73 mg, 0.5
mmol) and 3-phenyl-1-propanamine (95 mg, 0.7 mmol)
5s
1
2
was stirred at 140 °C for 20 h. The product
was isolated
by a column chromatography on silica gel (n-hexane/ethyl
acetate = 50:1 to 1:1; 92 mg, 75%). TLC; Rf = 0.2 (50%
EtOAc in hexanes). Data for 5s: δ 7.30–7.23 (m, 2H), 7.22–
7.12 (m, 3H), 6.73 (br s, 1H), 4.08 (dd, J = 9.0, 4.8 Hz, 1H),
3.28 (dd, J = 8.9, 4.8 Hz, 1H), 2.63 (t, J = 7.5 Hz, 2H), 2.50–
2.37 (m, 1H), 2.37–2.19 (m, 2H), 2.16–2.05 (m, 1H), 1.84
(quintet, J = 7.4 Hz, 2H) ppm; 13C{1H} NMR (100 MHz,
CDCl3) δ 179.5, 172.1, 141.4, 128.4, 128.3, 126.0, 57.1, 39.3,
33.2, 30.8, 29.4, 25.7 ppm; GC-MS for C14H18N2O2, m/z =
246 (M+); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C14H18N2O2H 247.1441; Found 247.1408.
3
4
5
6
7
8
9
N-(3,5-Dimethoxybenzyl)-4-
(trifluoromethyl)benzenamine (5p). A chlorobenzene (2.0
mL) solution of complex
1
(7 mg, 0.75 mol %), L1 (8 mg,
10 mol %), 4-trifluoromethylaniline (81 mg, 0.5 mmol)
and 3,5-dimethoxybenzylamine (117 mg, 0.7 mmol) was
stirred at 140 °C for 20 h. The product 5p was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
150:1 to 40:1; 58 mg, 37%). TLC; Rf = 0.4 (30% EtOAc in
hexanes). Data for 5p: 1H NMR (400 MHz, CDCl3) δ 7.39 (d,
J = 8.6 Hz, 2H), 6.63 (d, J = 8.6 Hz, 2H), 6.51 (d, J = 2.3 Hz,
2H) 6.39 (t, J = 2.3 Hz, 1H), 4.55 (br s, 1H), 4.30 (s, 2H),
3.78 (s, 6H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 161.1,
150.3, 140.9, 126.6 (q, JCF = 3.8 Hz), 124.9 (q, JCF = 270.6
Hz), 119.2 (q, JCF = 32.6 Hz), 112.1 105.2, 99.1, 55.3, 48.0
ppm; GC-MS for C16H16F3NO2, m/z = 311 (M+); HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C16H6F3NO2H 312.1206;
Found 312.1207.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3-(4-Methoxybenzylamino)piperidine-2,6-dione (5t).
A
chlorobenzene (2.0 mL) solution of complex (7 mg, 0.75
1
mol %), L1 (8 mg, 10 mol %), L-glutamine (73 mg, 0.5
mmol) and 4-methoxybenzylamine (96 mg, 0.7 mmol) was
stirred at 140 °C for 20 h. The product 5t was isolated by a
column chromatography on silica gel (n-hexane/ethyl ace-
tate = 50:1 to 1:1; 87 mg, 70%). TLC; Rf = 0.2 (50% EtOAc
in hexanes). Data for 5t δ 7.18 (d, J = 8.5 Hz, 2H), 6.92 (br
s, 1H), 6.83 (d, J = 8.5 Hz, 2H), 4.40–4.29 (m, 2H), 4.13 (dd,
J = 9.0, 4.7 Hz, 1H), 3.77 (s, 3H), 2.53–2.41 (m, 1H), 2.34–
2.20 (m, 2H), 2.20–2.09 (m, 1H), 1.87 (br s, 1H) ppm;
13C{1H} NMR (100 MHz, CDCl3) δ 179.5, 172.2, 158.8,
130.1, 128.9, 113.8, 57.0, 55.1, 42.7, 29.2, 25.5 ppm; GC-MS
for C13H16N2O3, m/z = 248 (M+); HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C13H16N2O3H 249.1334; Found 249.1202.
9-Ethyl-N-hexyl-9H-carbazol-3-amine (5q). A chloro-
benzene (2.0 mL) solution of complex
1
(7 mg, 0.75 mol
%), L1 (8 mg, 10 mol %), 3-amino-9-ethylcarbazole (105
mg, 0.5 mmol) and 1-hexamine (71 mg, 0.7 mmol) was
stirred at 140 °C for 20 h. The product 5q was isolated by a
column chromatography on silica gel (n-hexane/EtOAc =
150:1 to 40:1; 103 mg, 70%). TLC; Rf = 0.4 (50% EtOAc in
1
hexanes). Data for 5q: H NMR (400 MHz, CDCl3) δ 8.09–
8.04 (m, 1H), 7.48–7.42 (m, 1H), 7.40–7.34 (m, 2H), 7.26
(d, J = 7.3 Hz, 1H), 7.19 (dd, J = 7.3, 1.2 Hz, 1H), 6.91 (dd, J
= 8.6, 2.3 Hz, 1H), 4.32 (q, J = 7.2 Hz, 2H), 3.40 (br s, 1H),
3.25 (t, J = 7.2 Hz, 2H), 1.72 (quintet, J = 7.4 Hz, 2H), 1.55–
1.45 (m, 2H), 1.42 (t, J = 7.2 Hz, 3H), 1.41–1.33 (m, 4H),
1.12–0.92 (m, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ
141.9, 140.2, 133.9, 125.2, 123.6, 122.6, 120.3, 117.8,
114.6, 109.0, 108.3, 103.3, 45.7, 37.4, 31.7, 29.7, 27.0, 22.6,
14.0, 13.8 ppm; GC-MS for C20H26N2, m/z = 294 (M+);
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C20H26N2H
295.2169; Found 295.2167.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Experimental procedures, spectroscopic data and NMR spec-
tra (PDF)
AUTHOR INFORMATION
(R)-3-Ethyl-3-(4-(3,4,5-
trimethoxybenzylamino)phenyl)piperidine-2,6-dione (5r).
A chlorobenzene (2.0 mL) solution of complex
0.75 mol %), L1 (8 mg, 10 mol %), (R)-(+)-
aminoglutethimide (116 mg, 0.5 mmol) and 3,4,5-
trimethoxybenzylamine (138 mg, 0.7 mmol) was stirred at
140 °C for 20 h. The product 5r was isolated by a column
chromatography on silica gel (n-hexane/ethyl acetate =
100:1 to 1:1; 82 mg, 40%), [a]ꢁꢀꢁ = +148.2 (c = 0.2 in
Corresponding Author
* E-mail: chae.yi@marquette.edu
1
(7 mg,
ORCID
Chae S. Yi: 0000-0002-4504-1151
Notes
The authors declare no competing financial interest.
CH2Cl2); TLC; Rf = 0.2 (50% EtOAc in hexanes). Data for 5r
:
ACKNOWLEDGMENT
δ 7.98 (br s, 1H), 7.07 (d, J = 8.7 Hz, 2H), 6.64 (d, J = 8.7
Hz, 2H), 6.59 (s, 2H), 4.24 (s, 2H), 3.83 (s, 9H), 2.62–2.52
(m, 1H), 2.44 (dd, J = 13.2, 4.9 Hz, 1H), 2.31 (ddd, J = 14.2,
4.8, 2.7 Hz, 1H), 2.16 (dd, J = 13.8, 4.8 Hz, 1H), 1.99 (sext, J
= 7.4 Hz, 1H), 1.87 (sextet, J = 7.4 Hz, 1H), 0.85 (t, J = 7.4
Hz, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3) δ 175.5,
172.5, 153.4, 147.0, 137.1, 134.5, 127.1, 113.4, 113.4,
104.4, 60.8, 56.1, 50.2, 48.9, 32.9, 29.3, 26.9, 9.0 ppm; GC-
MS for C23H28N2O5, m/z = 412 (M+); HRMS (IT-TOF/ESI)
Calcd for C23H28N2O5-H ([M-H]-): 411.1925, Found:
411.1908.
Financial support from the National Science of Foundation
(CHE-1358439, CHE-1664652) and National Institute of
Health General Medical Sciences (R15 GM109273) is grateful-
ly acknowledged.
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A
1
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The Journal of Organic Chemistry
Page 16 of 18
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