Palladium-catalyzed cross-coupling reactions of organogold(i) phosphanes with allylic electrophiles

Article abstract of DOI:10.1039/c2ob06788a

Aryl and alkenylgold(i) phosphanes react regioselectively with allylic electrophiles such as cinnamyl and geranyl halides (bromide, chloride and acetates) under palladium catalysis in THF at 80 °C to afford the α-substitution product with moderate to high yields. When the reaction is performed with a chiral enantiopure secondary acetate, the α-substituted cross-coupling product is obtained with complete inversion of the stereochemistry.

Full text of DOI:10.1039/c2ob06788a

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PAPER
Palladium-catalyzed cross-coupling reactions of organogold(I) phosphanes
with allylic electrophiles†‡
Miguel Peña-López, Miguel Ayán-Varela, Luis A. Sarandeses* and José Pérez Sestelo*
Received 24th October 2011, Accepted 6th December 2011
DOI: 10.1039/c2ob06788a
Aryl and alkenylgold(I) phosphanes react regioselectively with allylic electrophiles such as cinnamyl and
geranyl halides (bromide, chloride and acetates) under palladium catalysis in THF at 80 °C to afford the
α-substitution product with moderate to high yields. When the reaction is performed with a chiral
enantiopure secondary acetate, the α-substituted cross-coupling product is obtained with complete
inversion of the stereochemistry.
report the reactivity of gold(I) organometallics with allylic elec-
trophiles under palladium catalysis.
Introduction
During recent years the use of gold reagents in organic synthesis
has increased exponentially following the discovery that cationic
complexes can catalyze the nucleophilic addition to unsaturated
C–C bonds.1 In this reaction gold(I) organometallics are syn-
thetic intermediates that usually suffer protodeauration to regen-
erate the gold(I) catalyst, but in some cases can be isolated2 and
even used in further organic transformations.3 Although the
properties and reaction patterns of gold compounds have been
studied throughout the last few decades,4 their utility in organic
synthesis is very limited probably due to their cost and low
nucleophilicity.5 Nowadays, transition metal-catalyzed reactions
offer a new opportunity for discovering novel synthetic trans-
formations using gold reagents in stoichiometric or catalytic
amounts.6 Recently, important contributions from different
groups have demonstrated that gold organometallics are useful
reagents in metal-catalyzed cross-coupling reactions.7 In our
group, we reported that organogold(I) phosphanes (RAuPPh3,
R = alkyl, alkynyl, alkenyl and aryl) react efficiently with aryl
halides (iodides, bromides and triflates), β-bromostyrene, benzyl
bromide and benzoyl chloride under palladium catalysis.8 The
main features of gold organometallics in this reaction are the
stability in air atmosphere, reactivity at room temperature, and
high chemoselectivity. These findings confirm organogold(I)
compounds as useful reagents for transmetalating organic groups
to palladium, and the possibility to develop gold-palladium cata-
lyzed processes. As part of a project aimed at studying the utility
of gold organometallics in metal-catalyzed reactions, we herein
The allylic substitution reaction is a key transformation in
organic synthesis due to the high reactivity and bidentate electro-
philicity of allylic substrates.9 The control of the regio- and
stereoselectivity are fundamental aspects that can be modulated
by selecting the reaction partners (nucleophile, catalyst or allylic
electrophile). Transition metal-catalyzed cross-coupling reactions
of allylic substrates involving the oxidative addition, transmeta-
lation and reductive elimination sequence have been performed
using several organometallics and provide a synthetically useful
methodology.10 However, the reactivity of gold organometallics
with allylic electrophiles is limited to some isolated examples.
First, Blum reported a palladium-catalyzed cross-coupling of an
alkenylgold(I) phosphane, obtained by alkyne carboauration,
with allyl bromide.6c More recently, Hashmi reported that
alkenylgold(I) phosphane, prepared by gold-catalyzed cyclization
of an allenoate, react with allyl iodide under palladium catalysis,
but other allylic electrophiles such as allyl bromide or cinnamyl
bromide and acetate failed.7b In a different approach, Blum has
also reported a dual-catalytic (Au–Pd) cross-coupling reaction
where an alkenyl gold phosphane, intermediate in a gold-cata-
lyzed cyclization, reacts with an allyl palladium complex.6d
Results and discussion
Guided by our experience in allylic cross-coupling reactions,11
we decided to study the reactivity of organogold(I) phosphanes
(RAuPPh3) with allylic electrophiles. Gold(I) organometallics
(RAuL) are air stable compounds that can be prepared from
organolithium, Grignard reagents, or boronic acids.12 In our first
reaction, we observed that phenyl(triphenylphosphine)gold
(PhAuPPh3, 1a, 110 mol %) reacts slowly with (E)-cinnamyl
bromide (2a) at room temperature affording, after 24 h, the SN2
product 3a in 15% yield (Table 1, entry 1). However, longer
reaction times (up to 48h) or higher temperatures did not
Departamento de Química Fundamental, Universidade da Coruña,
E-15071 A Coruña, Spain. E-mail: sestelo@udc.es, qfsarand@udc.es;
Fax: +34 981 167 065
†This paper is dedicated to the memory of Prof. Rafael Suau
‡Electronic supplementary information (ESI) available. See DOI:
10.1039/c2ob06788a
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Table 1 Reaction of phenyl(triphenylphosphine)gold with (E)-
Table 2 Reaction of organogold(I) phosphanes with (E)-cinnamyl
bromide
cinnamyl halidesa
Entry
1
R
Product
Yield (%)a
93
Entry
X
Catalyst
T/°C
Yield (%)b
(1b)
(1c)
3b
1
2
3
4
5
6
7
8
Br (2a)
Br (2a)
Br (2a)
Br (2a)
Br (2a)
Br (2a)
Br (2a)
Cl (2b)
Cl (2b)
Cl (2b)
OAc (2c)
OAc (2c)
OAc (2c)
OAc (2c)
No cat.
No cat.
25
80
25
25
80
80
80
80
80
80
80
80
80
80
15
15
20
18
75
80
78
—
84
77
83
—
84
85c
Pd(PPh3)2Cl2
Pd2(dba)3
Pd(PPh3)2Cl2
Pd2(dba)3
Pd(PPh3)4
No cat.
Pd(PPh3)2Cl2
Pd2(dba)3
Pd(PPh3)2Cl2
No cat.
2
3c
76
3
4
(1d)
(1e)
3d
3e
83
56
9
10
11
12
13
14
Pd2(dba)3
Pd(PPh3)2Cl2
5
6
(1f)
(1g)b
3f
3gc
75
87
a All the reactions were conducted using 110 mol % of PhAuPPh3.
b Isolated yield. c Reaction performed in THF/H2O (1 : 1).
7
(1h)d
3he
90
1
a Isolated yield. b As a E/Z (82 : 18) mixture by H NMR. c As a 4E/4Z
1
1
(82 : 18) mixture by H NMR. d As a E/Z (92 : 8) mixture by H NMR.
improve the transformation, producing significant amounts of the
biphenyl from oxidative dimerization of the organogold reagent
(Table 1, entry 2). When the coupling reaction was tried under
palladium catalysis at room temperature using 5 mol % of
Pd(PPh3)2Cl2 or Pd2(dba)3 complexes the yield remained unal-
tered, but at 80 °C the α-substitution product 3a was obtained in
e As a 4E/4Z (91 : 9) mixture by 1H NMR.
1
without isomerization by H NMR (Table 2, entry 5). Likewise,
the cross-coupling reaction using the stereodefined (E/Z =
82 : 18) 1-heptenylgold phosphane 1g, proceeded efficiently to
give the (1E,4E)-diene 3g in 87% as major stereoisomer with
retention of the configuration (4E/4Z = 82 : 18, Table 2, entry 6).
When the reaction was performed using the styrylgold reagent
1h (E/Z = 92 : 8), the coupling product 3h (4E/4Z = 91 : 9) was
also obtained stereospecifically in 90% yield (Table 2, entry 7).
These results are particularly interesting since several alkenyl-
gold species have been isolated as intermediates in different
gold-catalyzed reactions, and the development of metal-cata-
lyzed tandem reactions using one or two metals is an attractive
goal in organic synthesis.6
In the course of our research we also tested the ability of orga-
nogold reagents for transferring alkynyl and alkyl groups to
allylic electrophiles under palladium catalysis. However, the
reaction of phenylethynyl(triphenylphosphine)gold (1i) with cin-
namyl bromide at 80 °C using 5 mol % of Pd(PPh3)2Cl2, only
led to the diyne resulting from dimerization of the organogold
reagent. The same result was reproduced using Pd2(dba)3 as cata-
lyst and when cinnamyl chloride or acetate were used as electro-
philes. This reactivity contrasts with the high efficiency
exhibited by 1i in the palladium-catalyzed cross-coupling reac-
tion with aryl, benzyl and benzoyl electrophiles.8 On the other
hand, we studied the reactivity of alkylgold reagents using
n-butyl(triphenylphosphine)gold (1j). In this case, the reaction
of 1j with cinnamyl bromide provided the reductive homocou-
pling of the starting bromide in 76% yield.14 A result related
with the reductive dimerization observed in the palladium-cata-
lyzed cross-coupling of 1j with 4-iodotoluene.8
1
high yields (75–80%, Table 1, entries 5–7). The H NMR of the
reaction crude showed that the reaction proceeds with high
regioselectivity (the γ-substitution product was undetectable) and
without isomerization of the double bond. When the reaction
conditions were extended to other cinnamyl derivatives such as
chloride (2b) and acetate (2c) the α-coupling product 3a was
obtained as a single product with high yields (77–84%) using
several Pd(0) or Pd(II) complexes (Table 1, entries 8–13).13
Besides the high efficiency and regioselectivity observed, it is
interesting to note that PhAuPPh3 is a stable reagent at air atmos-
phere and the reaction with cinnamyl acetate (2c) can be per-
formed in aqueous media (1 : 1, THF/H2O) with similar yield
(85%, Table 1, entry 14).
Encouraged by these results, we explored the versatility of the
reaction using substituted arylgold reagents. In this case we
found that the reaction of o-methoxyphenyl (1b), p-trifluoro-
methylphenyl (1c) and m-nitrophenyl (1d) gold phosphanes with
(E)-cinnamyl bromide gave regioselectively the trans α-substi-
tuted products 3b–d in high yields (76–93%, Table 2, entries
1–3). Analogously, the reaction using the heteroarylgold(I)
reagent 1e, furnished with the furyl group, afforded the coupling
product 3e in 56% yield (Table 2, entry 4). In this way we
demonstrate that the allylic cross-coupling can be efficiently per-
formed with ortho-, meta- and para-substituted arylgold reagents
furnished with electron donating or withdrawing groups.
Our next step was to study the reactivity of alkenylgold(I)
organometallics. Under the previously developed conditions, the
reaction of vinylgold(I) phosphane 1f with cinnamyl bromide
gave the 1,4-diene 3f in 75% yield as a single reaction product
To study the regio- and stereoselectivity of the allylic substi-
tution reaction using organogold(I) reagents, 1-phenylallyl
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Table 3 Reaction of organogold(I) phosphanes with geranyl
derivatives
Entry
X
R
Product
Yield (%)a
1
2
3
4
Br (6a)
Cl (6b)
OAc (6c)
Br (6a)
Ph
Ph
Ph
(1a)
(1a)
(1a)
(1b)
7a
7a
7a
7b
60
50
52
51
Scheme 1 Reaction of phenyl(triphenylphosphine)gold with 1-phenyl-
allyl acetate (4) and (Z)-cinnamyl bromide (5).
acetate (4) and (Z)-cinnamyl bromide (5)15 were chosen as
allylic electrophiles. Interestingly, the palladium-catalyzed reac-
tion of 1a with 4 afforded the SN2′ type product (3a) in 90%
yield as the only regioisomer (Scheme 1). Moreover, the reaction
of 1a with 5 provided the α-coupling product (SN2) in high
yield (93%), but with complete isomerization of the double bond
to the most stable trans isomer. These results support the for-
mation of a π-allylpalladium intermediate during the cross-coup-
ling reaction.
5
Br (6a)
(1c)
7c
45
6
7
Br (6a)
Br (6a)
(1d)
(1e)
7d
7e
40
40
8
9
Br (6a)
Br (6a)
(1g)b
(1h)d
7gc
7he
89
54
To expand the scope of the methodology, we tested the reac-
tivity of aliphatic allylic electrophiles such as geranyl bromide
(6a), a substrate previously explored in metal-catalyzed cross-
coupling reactions of organometallic reagents with allylic eletro-
philes.11 Under the previously developed conditions, the reaction
of PhAuPPh3 with 6a in the presence of Pd(PPh3)2Cl2 (5 mol%)
as catalyst afforded the α-coupling product 7a in 60% yield as
a Isolated yield. b As a E/Z (82 : 18) mixture by 1H NMR. c As a E/Z
(84 : 16) mixture by H NMR. d As a E/Z (92 : 8) mixture by H NMR.
1
1
e As a E/Z (92 : 8) mixture by 1H NMR.
1
major regioisomer with only traces (less than 2% by H NMR)
of the γ-coupling product (Table 3, entry 1). Analogously, the
reaction using geranyl chloride or acetate as electrophiles pro-
vided similar yields and other reaction conditions varying the
catalyst [Pd(PPh3)2Cl2 or Pd2(dba)3], or the temperature did not
improve the efficiency of the tranformation (50% and 52%,
Table 3, entries 2 and 3, respectively). The reaction of the aryl-
gold reagents 1b–e with geranyl bromide provided the α-cross-
coupling products in moderate yields (40–51%, Table 3, entries
4–7). However, the reaction using the heptenylgold reagent 1g
afforded the (E,E)-1,4-diene (E/Z = 84 : 16) coupling product
stereoselectively in 89% yield, and using the (E)-styrylgold
phosphane 1h the coupling product 7h (E/Z = 92 : 8) was iso-
lated in 54% yield (Table 3, entries 8 and 9).
In an effort to determine if the additional olefin present in the
geranyl derivatives was responsible for the lower isolated yields,
we also tested the reactivity of allylic bromide derived from
phytol.16 However, the reaction of PhAuPPh3 provided the SN2
product in a similar yield (61%), what seems to indicate that the
lower yields obtained with geranyl derivatives can also be attrib-
uted to the structure of the allylic moiety.
To gain insight into the reaction mechanism of this palladium-
catalyzed allylic substitution, we tested the reactivity of the orga-
nogold reagents with the enantiomerically pure (>99% ee)
secondary acetate (R)-(E)-8.17 In this case, the reaction of
PhAuPPh3 with (R)-(E)-8, using Pd2dba3 (5 mol %) at 80 °C
proceeded efficiently to afford the α-coupling product (S)-(E)-9
(>99% ee) in 83% yield with complete inversion of the configur-
ation (Scheme 2).13,18 This stereochemical result is coherent
with the general mechanism proposed for palladium-catalyzed
Scheme 2 Reaction of phenyl(triphenylphosphine)gold with secondary
acetate (R)-(E)-8.
allylic substitution using organometallic reagents,19 and can be
explained through a nucleophilic addition of the Pd(0) catalyst
with inversion, followed by a transmetallation and reductive
elimination with retention of configuration. In addition, these
results demonstrate the efficiency of the palladium-catalyzed
cross-coupling of organogold reagents with secondary allylic
acetates.
Conclusions
In summary, we have shown that aryl- and alkenylgold(I) phos-
phanes react regio- and stereoselectively with allylic electro-
philes such as cinnamyl halides and acetates and geranyl
bromide, under palladium catalysis at 80 °C, to afford the α-sub-
stituted cross-coupling product, in moderate to good yields.
When the reaction is performed with an enantiomerically pure
secondary acetate, the α-substituted product is obtained with
inversion of configuration. These results support the use of the
aryl and alkenylgold intermediates of gold-catalyzed reactions in
allylic palladium-catalyzed cross-coupling reactions. The main
features of this methodology relay in the air stability of the
1688 | Org. Biomol. Chem., 2012, 10, 1686–1694
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organogold reagents what opens the posibility to perform cross-
coupling reaction in water and in the presence of wide number of
functional groups. Further developments of this methodology are
currently underway in our laboratories.
P) = 13.9 Hz, 6 × CH), 140.0 (s, 3 × CH) ppm; 31P NMR
(121.5 MHz, C6D6) δ 43.99 (s) ppm; IR (ATR) 3051, 3006,
2922, 2851, 1571, 1478, 1434 cm−1; MS (EI) m/z (%): 536 (M+,
71), 459 (M+ − C6H5, 100); HRMS (EI) m/z: calcd for
C24H20PAu (M+) 536.0963, found 536.0944.
Experimental
2-Methoxyphenyl(triphenylphosphine)gold (1b)
General methods
Following the general procedure, 1b was isolated as a white
powder (69.3 mg, 0.122 mmol, 81%). M.p. 140–142 °C; 1H
NMR (300 MHz, C6D6) δ 3.65 (s, 3H), 6.89–7.00 (m, 10H),
7.22–7.33 (m, 2H), 7.44–7.51 (m, 6H), 8.09 (dt, J (C,P) = 1.9,
6.5 Hz, 1H) ppm; 13C NMR (75 MHz, C6D6) δ 55.0 (s, CH3),
110.0 (d, J (C,P) = 4.3 Hz, CH), 120.9 (d, J (C,P) = 6.0 Hz,
CH), 126.6 (s, CH), 128.7 (d, J (C,P) = 10.6 Hz, 6 × CH), 130.5
(d, J (C,P) = 2.1 Hz, 3 × CH), 131.6 (d, J (C,P) = 48.8 Hz, 3 ×
C), 134.3 (d, J (C,P) = 13.8 Hz, 6 × CH), 140.2 (s, CH), 160.5
(d, J (C,P) = 112.8 Hz, C), 166.1 (d, J (C,P) = 0.9 Hz, C) ppm;
31P NMR (121.5 MHz, C6D6) δ 44.25 (s) ppm; IR (ATR) 3054,
2944, 2828, 1566, 1479 cm−1; MS (EI) m/z (%): 566 (M+, 1),
459 (M+ − C7H7O, 2), 262 (M+ − C7H7OAu, 100); HRMS (EI)
m/z: calcd for C25H22OPAu (M+) 566.1068, found 566.1063.
Unless otherwise is stated, all reactions were conducted in flame-
dried glassware under a positive pressure of argon. Reaction
temperatures refer to external bath temperatures. Anhydrous THF
was obtained by distillation from the sodium/benzophenone. All
other commercially available reagents were used as received.
Organic extracts were dried over anhydrous MgSO4, filtered, and
concentrated by using a rotary evaporator at aspirator pressure
(20–30 mmHg). TLC was effected on silica gel 60 F254 (layer
thickness 0.2 mm) and components were located by observation
under UV light and/or by treating the plates with a phosphomo-
lybdic acid, or p-anisaldehyde reagent followed by heating.
Column chromatography was performed on silica gel
(230–400 mesh).20 NMR spectra were performed in a Bruker
Avance 300 spectrometer using the residual solvent signal as
internal standard. DEPT was used to assign carbon types. The
low resolution electron-impact mass spectra were measured on a
Thermo Finnigan Trace MS spectrometer at 70 eV. The high res-
olution mass spectra were measured on a Thermo Finnigan MAT
95XP spectrometer. Infrared spectra were taken with a Bruker
Vector 22 and with ATR (“attenuated total reflectance”). Optical
rotation values were determined at room temperature in a
JASCO DIP-1000 Digital polarimeter. HPLC analyses were per-
formed on an Agilent 1200 Series system by using a Daicel
CHIRALCEL OD-H column (0.46 cm Ø × 25 cm).
4-Trifluoromethylphenyl(triphenylphosphine)gold (1c)6c
Following the general procedure, 1c was isolated as a brown
powder (72.6 mg, 0.120 mmol, 79%). M.p. 155–157 °C; 1H
NMR (300 MHz, C6D6) δ 6.91–6.99 (m, 9H), 7.33–7.41 (m,
6H), 7.66 (d, J = 7.7 Hz, 2H), 7.95 (t, J = 6.3 Hz, 2H) ppm; 13
C
NMR (75 MHz, C6D6) δ 123.6 (m, 2 × CH), 127.6 (s, 3 × C),
128.9 (d, J (C,P) = 10.9 Hz, 6 × CH), 130.5 (s, C), 130.8 (d, J
(C,P) = 2.1 Hz, 2 × CH), 131.2 (s, C), 134.2 (d, J (C,P) = 13.7
Hz, 6 × CH), 139.9 (s, 3 × CH), 178.3 (d, J (C,P) = 116.8 Hz,
C) ppm; 31P NMR (121.5 MHz, C6D6) δ 43.62 (s) ppm; IR
(ATR) 3057, 1591, 1556, 1479, 1322 cm−1; MS (EI) m/z (%):
604 (M+, 1), 459 (M+ − C7H4F3, 3), 262 (M+ − C7H4F3Au,
100); HRMS (EI) m/z: calcd for C25H19F3PAu (M+) 604.0837,
found 604.0808.
General procedure for the preparation of organogold
compounds
To a cooled solution of Ph3PAuCl (75 mg, 0.152 mmol) in dry
THF (3 mL) at −20 °C, a solution of RLi or RMgBr
(0.182 mmol, 1.0–2.0 M) in THF was added dropwise. The
mixture was stirred 20 min, the cooling bath was removed, and
the reaction mixture stirred for 1 h at room temperature. The
solvent was evaporated under reduced pressure and benzene
(5 mL) was added. The mixture was filtered through Celite, con-
centrated at reduced pressure to dryness, washed with pentane
and dried. The solid was re-extracted with a minimum of
benzene, filtered, washed with pentane and dried under high-
vacuum.
3-Nitrophenyl(triphenylphosphine)gold (1d)21
Cs2CO3 (236.9 mg, 0.727 mmol) and Ph3PAuCl (180 mg,
0.363 mmol) were added successively to a solution of 3-nitro-
phenylboronic acid (121.4 mg, 0.727 mmol) in dry isopropyl
alcohol (5 mL). The resultant white suspension was stirred at
50 °C for 24 h and taken to dryness via rotary evaporation. The
solid was extracted with benzene, filtered through Celite, concen-
trated in vacuo to dryness, washed with pentane and dried. The
solid was re-extracted with a minimum of benzene, filtered,
washed with pentane and dried under high-vacuum, to give the
organogold phosphane 1d as a white powder (192.5 mg,
0.331 mmol, 91%). M.p. 170–171 °C; 1H NMR (300 MHz,
CDCl3) δ 7.41 (dd, J = 7.3, 8.1 Hz, 1H), 7.46–7.64 (m, 15H),
7.87–7.94 (m, 2H), 8.45 (br s, 1H) ppm; 13C NMR (75 MHz,
CDCl3) δ 120.5 (s, CH), 127.5 (s, CH), 129.2 (d, J (C,P) = 10.8
Hz, 6 × CH), 130.2 (s, C), 130.9 (s, C), 131.3 (d, J (C,P) = 2.2
Hz, CH), 133.5 (s, CH), 134.3 (d, J (C,P) = 13.8 Hz, 6 × CH),
146.0 (s, 3 × CH), 147.5 (s, 3 × C) ppm; 31P NMR (121.5 MHz,
Phenyl(triphenylphosphine)gold (1a)21
Following the general procedure, 1a was isolated as a white
powder (74.8 mg, 0.139 mmol, 92%). M.p. 160–161 °C; 1H
NMR (300 MHz, C6D6) δ 6.88–6.97 (m, 9H), 7.26 (t, J = 7.4
Hz, 1H), 7.37–7.44 (m, 6H), 7.52 (t, J = 7.5 Hz, 2H), 8.11 (d, J
= 7.0 Hz, 2H) ppm; 13C NMR (75 MHz, C6D6) δ 125.9 (s, 2 ×
CH), 127.5 (s, 3 × C), 127.7 (s, C), 127.7 (br s, 2 × CH), 128.7
(d, J (C,P) = 10.5 Hz, 6 × CH), 130.6 (br s, CH), 134.2 (d, J (C,
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CDCl3) δ 43.36 (s) ppm; IR (ATR) 3052, 2923, 2852, 1509,
1.61–1.71 (m, 2H), 2.56 (q, J = 6.9 Hz, 2H), 6.43–6.56 (m, 1H),
6.85–6.97 (m, 9H), 7.35–7.43 (m, 6H), 7.53 (dd, J = 18.4, 5.1
Hz, 1H) ppm; 13C NMR (75 MHz, C6D6) δ 14.0 (s, CH3), 22.8
(s, 2 × CH2), 30.2 (s, CH2), 31.7 (s, CH2), 128.7 (d, J (C,P) =
10.5 Hz, 6 × CH), 130.5 (s, CH), 131.7 (d, J (C,P) = 47.2 Hz, 3
× C), 134.2 (d, J (C,P) = 13.8 Hz, 6 × CH), 144.4 (s, CH), 146.4
(s, 3 × CH) ppm; 31P NMR (121.5 MHz, C6D6) δ 45.41 (s)
ppm; IR (ATR) 3053, 2952, 2916, 2849, 1583, 1479 cm−1; MS
1479, 1435 cm−1; MS (EI) m/z (%): 581 (M+, 3), 459 (M+
−
C6H4NO2, 12), 262 (M+ − C7H4F3Au, 100); HRMS (EI) m/z:
calcd for C24H19NO2PAu (M+) 581.0813, found 581.0823.
2-Furyl(triphenylphosphine)gold (1e)22
Following the general procedure, 1e was isolated as a white
powder (74.2 mg, 0.141 mmol, 93%). M.p. 157–159 °C; 1H
NMR (300 MHz, C6D6) δ 6.68 (dd, J = 1.6, 3.0 Hz, 1H),
6.83–7.00 (m, 10H), 7.25–7.33 (m, 6H), 7.90 (d, J = 1.5 Hz,
1H) ppm; 13C NMR (75 MHz, C6D6) δ 108.4 (s, CH), 118.9 (br
s, CH), 127.6 (s, 3 × C), 128.8 (d, J (C,P) = 10.8 Hz, 6 × CH),
130.6 (d, J (C,P) = 2.3 Hz, 51.5 Hz, C), 130.8 (d, J (C,P) = 2.3
Hz, CH), 134.2 (d, J (C,P) = 13.8 Hz, 6 × CH), 144.2 (s, 3 ×
CH) ppm; 31P NMR (121.5 MHz, C6D6) δ 43.90 (s) ppm; IR
(ATR) 3062, 1478, 1433, 1350 cm−1; MS (EI) m/z (%): 526
(M+, 1), 459 (M+ − C4H3O, 2), 262 (M+ − C4H3OAu, 100);
HRMS (EI) m/z: calcd for C22H18OPAu (M+) 526.0755, found
526.0740.
(EI) m/z (%): 556 (M+, 1), 459 (M+ − C7H13, 2), 262 (M+
−
C7H13Au, 100).
(E)-2-Phenylethenyl(triphenylphosphine)gold (1h)21
Following the general procedure, 1h was isolated as a brown
powder (81.2 mg, 0.144 mmol, 95%, E/Z 92 : 8).
1
M.p. 144–146 °C; H NMR (300 MHz, C6D6) δ 6.88–6.97 (m,
9H), 7.04 (t, J = 7.3 Hz, 1H), 7.21 (t, J = 7.6 Hz, 2H), 7.31–7.45
(m, 6H), 7.51 (d, J = 19.2 Hz, 1H), 7.66 (d, J = 7.3 Hz, 2H),
8.49 (d, J = 19.2 Hz, 1H) ppm; 13C NMR (75 MHz, C6D6) δ
125.8 (s, 2 × CH), 126.0 (s, CH), 128.0 (s, 3 × C), 128.4 (s, 2 ×
CH), 128.8 (d, J (C,P) = 10.6 Hz, 6 × CH), 130.7 (d, J (C,P) =
1.8 Hz, 2 × CH), 134.2 (d, J (C,P) = 13.8 Hz, 6 × CH), 141.4 (s,
C), 144.4 (s, 3 × CH) ppm; 31P NMR (121.5 MHz, C6D6) δ
Ethenyl(triphenylphosphine)gold (1f)6c
Following the general procedure, 1f was isolated as a white
powder (66.5 mg, 0.137 mmol, 90%). M.p. 124–125 °C; 1H
NMR (300 MHz, CDCl3) δ 5.49–5.57 (dd, J = 4.9, 20.7 Hz,
1H), 6.00–6.07 (dd, J = 4.9, 14.0 Hz, 1H), 7.15–7.26 (dd, J =
14.0, 20.7 Hz, 1H), 7.41–7.59 (m, 15H) ppm; 13C NMR
(75 MHz, CDCl3) δ 129.0 (d, J (C,P) = 10.9 Hz, 6 × CH), 130.7
(d, J (C,P) = 51.2 Hz, 3 × C), 131.2 (d, J (C,P) = 2.1 Hz, 3 ×
CH), 131.4 (s, CH2), 134.3 (d, J (C,P) = 13.7 Hz, 6 × CH),
168.0 (m, CH) ppm; 31P NMR (121.5 MHz, CDCl3) δ 45.09 (s)
ppm; IR (ATR) 3638, 3055, 2955, 1480, 1434 cm−1; MS (EI)
45.21 (s) ppm; IR (ATR) 3052, 2010, 1593, 1551, 1478 cm−1
;
MS (EI) m/z (%): 562 (M+, 1), 459 (M+ − C8H7, 4), 262 (M+ −
C8H7Au, 100); HRMS (EI) m/z: calcd for C26H22PAu (M+)
562.1125, found 562.1121.
2-Phenylethynyl(triphenylphosphine)gold (1i)23
Following the general procedure, 1i was isolated as a white
powder (84.3 mg, 0.150 mmol, 99%). M.p. 161–162 °C; 1H
NMR (300 MHz, C6D6) δ 6.84–6.98 (m, 9H), 7.02–7.08 (m,
3H), 7.19–7.26 (m, 6H), 7.84 (d, J = 7.9 Hz, 2H) ppm; 13C
NMR (75 MHz, C6D6) δ 126.1 (s, CH), 127.5 (s, C), 127.8 (s,
C), 128.1 (d, J (C,P) = 12.2 Hz, CH), 128.8 (d, J (C,P) = 11.2
Hz, CH), 129.9 (s, C), 130.6 (s, C), 130.8 (d, J (C,P) = 2.2 Hz,
CH), 132.4 (s, CH), 134.1 (d, J (C,P) = 13.9 Hz, CH) ppm; 31P
NMR (121.5 MHz, C6D6) δ 41.98 (s) ppm; IR (ATR) 3053,
2923, 2357, 1595, 1483, 1435, 1331 cm−1; MS (EI) m/z (%):
560 (M+, 18), 459 (M+ − C8H5, 1), 404 (100); HRMS (EI) m/z:
calcd for C26H20PAu (M+) 560.0963, found 560.0985.
m/z (%): 486 (M+, 5), 459 (M+
− C2H3, 17), 262
(M+ − C2H3Au, 100); HRMS (EI) m/z: calcd for C20H18PAu
(M+) 486.0806, found 486.0804.
(E)-1-Hepten-1-yl(triphenylphosphine)gold (1g)
Following the general procedure, a solution of (E)-1-heptenyl-
lithium, prepared from (E)-1-iodo-1-heptene (40.8 mg,
0.182 mmol, E/Z 82 : 18) and tBuLi (0.215 mL, 1.7 M in
pentane, 0.364 mmol), was added to a solution of Ph3PAuCl
(90 mg, 0.182 mmol) in THF (3 mL) and the resulting organo-
gold phosphane 1g was used directly in the palladium-catalyzed
cross-coupling reaction. Alternatively, 1g can be prepared from
(E)-1-heptenylboronic acid: Cs2CO3 (105.4 mg, 0.323 mmol)
and Ph3PAuCl (80 mg, 0.161 mmol) were added successively to
a solution of (E)-1-heptenylboronic acid (45.9 mg, 0.323 mmol)
in dry isopropyl alcohol (5 mL). The resultant white suspension
was stirred at 50 °C for 24 h and taken to dryness via rotary
evaporation. The solid was extracted with benzene, filtered
through Celite, concentrated in vacuo to dryness, washed with
pentane and dried. The solid was re-extracted with a minimum
of benzene, filtered, washed with pentane and dried under high-
vacuum, to give the organogold phosphane 1g as a pale brown
Butyl(triphenylphosphine)gold (1j)24
Following the general procedure, 1j was isolated as a colorless
oil (64.7 mg, 0.125 mmol, 83%).1H NMR (300 MHz, CDCl3) δ
0.97 (t, J = 7.3 Hz, 3H), 1.43–1.55 (m, 4H), 1.82–1.96 (m, 4H),
7.42–7.59 (m, 15H) ppm; 13C NMR (75 MHz, CDCl3) δ 14.3 (s,
CH3), 29.5 (d, J (C,P) = 5.3 Hz, CH2), 30.8 (d, J (C,P) = 94.9
Hz, CH2), 34.1 (d, J (C,P) = 3.8 Hz, CH2), 128.9 (d, J (C,P) =
10.3 Hz, CH), 130.7 (d, J (C,P) = 2.1 Hz, CH), 131.8 (d, J (C,P)
= 45.1 Hz, C), 134.3 (d, J (C,P) = 13.7 Hz, CH) ppm; 31P NMR
(121.5 MHz, CDCl3) δ 46.37 (s) ppm; IR (ATR) 3640, 2952,
2914, 2867, 1479, 1434, 1381 cm−1; MS (EI) m/z (%): 516 (M+,
7), 487 (M+ − C2H5, 15), 459 (M+ − C4H9, 100); HRMS (EI)
m/z: calcd for C22H24PAu (M+) 516.1276, found 516.1251.
1
solid (80.7 mg, 0.145 mmol, 90%). M.p. 91–93 °C; H NMR
(300 MHz, C6D6) δ 0.87 (t, J = 7.2 Hz, 3H), 1.26–1.49 (m, 4H),
1690 | Org. Biomol. Chem., 2012, 10, 1686–1694
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General procedure for the allylic palladium-catalyzed
cross-coupling reaction
(E)-1-Phenyl-3-(3-nitrophenyl)propene (3d)27
Following the general procedure, 3d was obtained as a white
powder (32.0 mg, 0.134 mmol, 83%). M.p. 53–54 °C; H NMR
1
To a mixture of the allylic substrate (1.0 equiv) and palladium
catalyst (5 mol %) in dry THF (4 mL), a THF solution of freshly
prepared RAuPPh3 (1.1 equiv) was added. The resulting mixture
was stirred at 80 °C under argon overnight until the starting
material was consumed (TLC). The reaction mixture was con-
centrated under reduced pressure and Et2O (20 mL) was added.
The ethereal phase was washed with brine (10 mL), dried with
MgSO4, filtered, and concentrated to a reduced volume at
reduced pressure. The residue was purified by flash chromato-
graphy to afford, after concentration and high-vacuum drying,
the corresponding allylic substitution product in the reported
yield.
(300 MHz, CDCl3) δ 3.67 (d, J = 6.9 Hz, 2H), 6.33 (dt, J = 6.9,
15.8 Hz, 1H), 6.52 (d, J = 15.8 Hz, 1H), 7.21–7.39 (m, 5H),
7.49 (t, J = 7.8 Hz, 1H), 7.59 (d, J = 7.7 Hz, 1H), 8.02–8.14 (m,
2H) ppm; 13C NMR (75 MHz, CDCl3) δ 38.9 (CH2), 121.4
(CH), 123.5 (CH), 126.2 (2 × CH), 127.2 (CH), 127.5 (CH),
128.6 (2 × CH), 129.3 (CH), 132.5 (CH), 134.9 (CH), 136.9
(C), 142.2 (C), 148.5 (C) ppm; IR (ATR) 3026, 2923, 2853,
1525, 1349 cm−1; MS (EI) m/z (%): 239 (M+, 100), 193 (M+ −
NO2, 21); HRMS (EI) m/z: calcd for C15H13NO2 (M+)
239.0941, found 239.0942.
(E)-1-Phenyl-3-(furan-2-yl)propene (3e)28
(E)-1,3-Diphenylpropene (3a)11b
Following the general procedure, 3e was obtained as a colorless
oil (11.6 mg, 0.063 mmol, 56%).1H NMR (300 MHz, CDCl3) δ
3.57 (d, J = 6.7 Hz, 2H), 6.09 (dd, J = 0.8, 3.2 Hz, 1H),
6.27–6.38 (m, 2H), 6.51 (d, J = 15.8 Hz, 1H), 7.20–7.40 (m,
6H) ppm; 13C NMR (75 MHz, CDCl3) δ 31.8 (CH2), 105.6
(CH), 110.3 (CH), 125.6 (CH), 126.2 (2 × CH), 127.3 (CH),
128.5 (2 × CH), 132.0 (CH), 137.2 (C), 141.4 (CH), 153.9 (C)
ppm; IR (ATR) 3082, 3059, 3027, 1596, 1504, 1448 cm−1; MS
(EI) m/z (%): 184 (M+, 100), 155 (M+ − CHO, 31); HRMS (EI)
m/z: calcd for C13H12O (M+) 184.0883, found 184.0874.
Following the general procedure, 3a was obtained as a colorless
oil (20.0 mg, 0.103 mmol, 75% from cinnamyl bromide;
22.4 mg, 0.115 mmol, 84% from cinnamyl chloride; 22.2 mg,
0.114 mmol, 83% from cinnamyl acetate).1H NMR (300 MHz,
CDCl3) δ 3.58 (d, J = 6.3 Hz, 2H), 6.39 (dt, J = 6.3, 15.7 Hz,
1H), 6.49 (d, J = 15.8 Hz, 1H), 7.20–7.41 (m, 10H) ppm; 13C
NMR (75 MHz, CDCl3) δ 39.4 (CH2), 126.1 (2 × CH), 126.2
(CH), 127.1 (CH), 128.5 (4 × CH), 128.7 (2 × CH), 129.2 (CH),
131.1 (CH), 137.5 (C), 140.2 (C) ppm; IR (ATR) 3059, 3025,
2897, 1600, 1494, 1451 cm−1; MS (EI) m/z (%): 194 (M+, 64),
117 (M+ − C6H5, 50); HRMS (EI) m/z: calcd for C15H14 (M+)
194.1090, found 194.1092.
(E)-1-Phenyl-1,4-pentadiene (3f)11b
Following the general procedure, 3f was obtained as a colorless
oil (13.3 mg, 0.092 mmol, 75%).1H NMR (300 MHz, CDCl3) δ
2.98 (tc, J = 1.4, 6.5 Hz, 2H), 5.05–5.17 (m, 2H), 5.86–5.99 (m,
1H), 6.24 (dt, J = 6.5, 15.8 Hz, 1H), 6.43 (d, J = 15.8 Hz, 1H),
7.18–7.39 (m, 5H) ppm; 13C NMR (75 MHz, CDCl3) δ 37.0
(CH2), 115.7 (CH2), 126.0 (2 × CH), 127.0 (CH), 128.2 (CH),
128.5 (2 × CH), 130.8 (CH), 136.5 (CH), 137.6 (C) ppm; IR
(ATR) 3080, 3061, 3026, 2924, 2853, 1736 cm−1; MS (EI) m/z
(%): 144 (M+, 53), 129 (M+ − CH3, 100); HRMS (EI) m/z:
calcd for C11H12 (M+) 144.0934, found 144.0927.
(E)-1-Phenyl-3-(2-methoxyphenyl)propene (3b)25
Following the general procedure, 3b was obtained as a colorless
oil (28.7 mg, 0.128 mmol, 93%).1H NMR (300 MHz, CDCl3) δ
3.57 (d, J = 5.3 Hz, 2H), 3.87 (s, 3H), 6.36–6.50 (m, 2H),
6.89–6.96 (m, 2H), 7.18–7.40 (m, 7H) ppm; 13C NMR
(75 MHz, CDCl3) δ 33.4 (CH2), 55.4 (CH3), 110.4 (CH), 120.6
(CH), 126.1 (2 × CH), 126.9 (CH), 127.4 (CH), 128.4 (2 × CH),
128.9 (CH), 129.9 (CH), 130.7 (CH), 137.8 (C), 157.3 (C) ppm;
IR (ATR) 3025, 2923, 2852, 1599, 1492, 1463, 1437 cm−1; MS
(EI) m/z (%): 224 (M+, 100), 193 (M+ − CH3O, 37); HRMS (EI)
m/z: calcd for C16H16O (M+) 224.1196, found 224.1194.
(1E,4E)-1-Phenyl-1,4-decadiene (3g)
Following the general procedure, 3g was obtained as a colorless
oil (23.6 mg, 0.110 mmol, 87%, 4E/4Z 82 : 18).1H NMR
(300 MHz, CDCl3) δ 0.91 (t, J = 6.8 Hz, 3H), 1.25–1.44 (m,
6H), 2.00–2.07 (m, 2H), 2.90–2.94 (m, 2H), 5.44–5.59 (m, 2H),
6.24 (dt, J = 6.5, 15.8 Hz, 1H), 6.41 (d, J = 15.8 Hz, 1H),
7.18–7.39 (m, 5H) ppm; 13C NMR (75 MHz, CDCl3) δ 14.1
(CH3), 22.6 (CH2), 29.2 (CH2), 31.4 (CH2), 32.6 (CH2), 35.9
(CH2), 126.0 (2 × CH), 126.9 (CH), 127.5 (CH), 128.5 (2 ×
CH), 129.4 (CH), 130.2 (CH), 132.1 (CH), 137.8 (C) ppm; IR
(ATR) 3025, 2955, 2923, 2871, 2854, 1494, 1448 cm−1; MS
(EI) m/z (%): 214 (M+, 47), 143 (M+ − C5H11, 100), 130 (M+ −
C6H12, 43); HRMS (EI) m/z: calcd for C16H22 (M+) 214.1716,
found 214.1711.
(E)-1-Phenyl-3-(4-trifluoromethylphenyl)propene (3c)26
Following the general procedure, 3c was obtained as a colorless
oil (25.9 mg, 0.099 mmol, 76%).1H NMR (300 MHz, CDCl3) δ
3.62 (d, J = 6.7 Hz, 2H), 6.34 (dt, J = 6.7, 15.8 Hz, 1H), 6.50
(d, J = 15.8 Hz, 1H), 7.21–7.40 (m, 7H), 7.59 (d, J = 8.0 Hz,
2H) ppm; 13C NMR (75 MHz, CDCl3) δ 39.1 (CH2), 125.4 (q, J
= 3.8 Hz, CF3), 125.4 (C), 126.2 (4 × CH), 127.4 (CH), 127.9
(CH), 128.6 (2 × CH), 128.9 (2 × CH), 131.9 (CH), 137.1 (C),
144.3 (d, J = 1.3 Hz, C) ppm; IR (ATR) 3029, 1620, 1601,
1497, 1323 cm−1; MS (EI) m/z (%): 262 (M+, 100), 193 (M+ −
CF3, 25); HRMS (EI) m/z: calcd for C16H13F3 (M+) 262.0964,
found 262.0957.
This journal is © The Royal Society of Chemistry 2012
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(1E,4E)-1,5-Diphenyl-1,4-pentadiene (3h)29
(E)-1-(3,7-Dimethylocta-2,6-dienyl)-4-(trifluoromethyl)benzene
(7c)
Following the general procedure, 3h was obtained as a colorless
oil (29.7 mg, 0.135 mmol, 90%, 4E/4Z 91 : 9).1H NMR
(300 MHz, CDCl3) δ 3.14 (t, J = 6.5 Hz, 2H), 6.31 (dt, J = 6.5,
15.8 Hz, 2H), 6.49 (d, J = 15.8 Hz, 2H), 7.20–7.41 (m, 10H)
ppm; 13C NMR (75 MHz, CDCl3) δ 36.2 (CH2), 126.1 (4 ×
CH), 127.1 (2 × CH), 128.2 (2 × CH), 128.5 (4 × CH), 131.0 (2
× CH), 137.6 (2 × C) ppm; IR (ATR) 3080, 3058, 3024, 1648,
1597, 1494, 1446 cm−1; MS (EI) m/z (%): 220 (M+, 100), 129
(M+ − C7H7, 43); HRMS (EI) m/z: calcd for C17H16 (M+)
220.1247, found 220.1245.
Following the general procedure, 7c was obtained as colorless
oil (17.0 mg, 0.060 mmol, 45%).1H NMR (300 MHz, CDCl3) δ
1.61 (s, 3H), 1.69 (s, 3H), 1.71 (s, 3H), 2.06–2.18 (m, 4H), 3.42
(d, J = 7.4 Hz, 2H), 5.07–5.14 (m, 1H), 5.29–5.35 (m, 1H), 7.29
(d, J = 7.9 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H) ppm; 13C NMR
(75 MHz, CDCl3) δ 16.1 (CH3), 17.7 (CH3), 25.7 (CH3), 26.5
(CH2), 34.0 (CH2), 39.6 (CH2), 121.9 (CH), 122.6 (C), 124.1
(CH), 125.2 (CH), 127.6 (CH), 128.6 (2 × CH), 131.6 (C),
137.3 (C), 145.9 (C) ppm; IR (ATR) 2967, 2918, 2856, 1618,
1321 cm−1; MS (EI) m/z (%): 282 (M+, 27), 213 (M+ − CF3,
28), 123 (M+ − C8H6F3, 100); HRMS (EI) m/z: calcd for
C17H21F3 (M+) 282.1590, found 282.1587.
(E)-1,4-Diphenyl-1,5-hexadiene (3j)14a
Following the general procedure, 3j was obtained as a colorless
oil (14.2 mg, 0.061 mmol, 76%).1H NMR (300 MHz, CDCl3) δ
2.66 (br t, J = 7.2 Hz, 2H), 3.45 (q, J = 7.4 Hz, 1H), 5.02–5.12
(m, 2H), 5.99–6.19 (m, 2H), 6.40 (br d, J = 15.8 Hz, 1H),
7.17–7.36 (m, 10H) ppm; 13C NMR (75 MHz, CDCl3) δ 39.0
(CH2), 50.0 (CH), 114.7 (CH2), 126.0 (2 × CH), 126.3 (CH),
126.9 (CH), 127.7 (2 × CH), 128.4 (2 × CH), 128.5 (2 × CH),
131.4 (2 × CH), 137.6 (C), 141.5 (CH), 143.7 (C) ppm; IR
(ATR) 3059, 2975, 2360, 2340, 1636, 1493 cm−1; MS (EI) m/z
(%): 234 (M+, 15), 117 (M+ − C9H9, 97), 115 (100); HRMS (EI)
m/z: calcd for C18H18 (M+) 234.1403, found 234.1395.
(E)-1-(3,7-dimethylocta-2,6-dien-1-yl)-3-nitrobenzene (7d)
Following the general procedure, 7d was obtained as a yellow
oil (29.0 mg, 0.112 mmol, 40%).1H NMR (300 MHz, CDCl3) δ
1.61 (s, 3H), 1.69 (s, 3H), 1.73 (s, 3H), 2.05–2.19 (m, 4H), 3.47
(d, J = 7.3 Hz, 2H), 5.07–5.14 (m, 1H), 5.30–5.37 (m, 1H),
7.41–7.54 (m, 2H), 8.03–8.07 (m, 2H) ppm; 13C NMR
(75 MHz, CDCl3) δ 16.2 (CH3), 17.7 (CH3), 25.7 (CH3), 26.5
(CH2), 33.8 (CH2), 39.6 (CH2), 120.9 (CH), 121.3 (CH), 123.2
(CH), 123.9 (CH), 129.1 (CH), 132.0 (C), 134.6 (CH), 138.0
(C), 143.8 (C), 148.4 (C) ppm; IR (ATR) 2961, 2923, 2854,
1728, 1528 cm−1; MS (EI) m/z (%): 259 (M+, 9), 149 (M+
−
(E)-3,7-Dimethyl-1-phenyl-2,6-octadiene (7a)11b
C6H4NO2, 45), 69 (100); HRMS (EI) m/z: calcd for C16H21NO2
(M+) 259.1567, found 259.1569.
Following the general procedure, 7a was obtained as colorless
oil (19.0 mg, 0.089 mmol, 60% from geranyl bromide; 15.8 mg,
0.074 mmol, 50% from geranyl chloride; 16.4 mg, 0.077 mmol,
52% from geranyl acetate).1H NMR (300 MHz, CDCl3) δ 1.63
(s, 3H), 1.71 (s, 3H), 1.74 (s, 3H), 2.06–2.18 (m, 4H), 3.39 (d, J
= 7.3 Hz, 2H), 5.11–5.18 (m, 1H), 5.34–5.40 (m, 1H),
7.17–7.22 (m, 3H), 7.27–7.33 (m, 2H); 13C NMR (75 MHz,
CDCl3) δ 16.1 (CH3), 17.7 (CH3), 25.7 (CH3), 26.6 (CH2), 34.2
(CH2), 39.7 (CH2), 123.0 (CH), 124.3 (CH), 125.7 (CH), 128.3
(2 × CH), 128.3 (2 × CH), 131.5 (C), 136.2 (C), 141.8 (C) ppm;
IR (ATR) 3029, 2968, 2916, 2856, 1495, 1453 cm−1; MS (EI)
m/z (%): 214 (M+, 76), 145 (M+ − C5H9, 100), 91 (M+ − C9H15,
25); HRMS (EI) m/z: calcd for C16H22 (M+) 214.1716, found
214.1710.
(E)-2-(3,7-Dimethylocta-2,6-dienyl)furan (7e)31
Following the general procedure, 7e was obtained as a colorless
oil (11.8 mg, 0.058 mmol, 40%).1H NMR (300 MHz, CDCl3) δ
1.62 (s, 3H), 1.70 (s, 6H), 2.03–2.16 (m, 4H), 3.36 (d, J = 7.1
Hz, 2H), 5.09–5.14 (m, 1H), 5.32–5.37 (m, 1H), 5.96–5.98 (m,
1H), 6.28–6.30 (dd, J = 1.8, 3.1 Hz, 1H), 7.30–7.32 (m, 1H)
ppm; 13C NMR (75 MHz, CDCl3) δ 16.1 (CH3), 17.7 (CH3),
25.7 (CH3), 26.6 (CH2), 27.0 (CH2), 39.6 (CH2), 104.6 (CH),
110.1 (CH), 119.2 (CH), 124.1 (CH), 131.5 (C), 137.6 (C),
140.9 (CH), 155.3 (C) ppm; IR (ATR) 2966, 2920, 2855, 1594,
1505 cm−1; MS (EI) m/z (%): 204 (M+, 13), 162 (M+ − C3H6,
2), 69 (100); HRMS (EI) m/z: calcd for C14H20O (M+)
204.1509, found 204.1508.
(E)-1-(3,7-Dimethylocta-2,6-dienyl)-2-methoxybenzene (7b)30
Following the general procedure, 7b was obtained as colouless
oil (13.7 mg, 0.056 mmol, 51%).1H NMR (300 MHz, CDCl3) δ
1.61 (s, 3H), 1.69 (s, 3H), 1.71 (s, 3H), 2.01–2.19 (m, 4H), 3.34
(d, J = 7.3 Hz, 2H), 3.84 (s, 3H), 5.08–5.18 (m, 1H), 5.33 (t, J =
7.3 Hz, 1H), 6.84–6.92 (m, 2H), 7.13–7.24 (m, 2H) ppm; 13C
NMR (75 MHz, CDCl3) δ 16.0 (CH3), 17.7 (CH3), 25.7 (CH3),
26.7 (CH2), 28.1 (CH2), 39.8 (CH2), 55.3 (CH3), 110.1 (CH),
120.4 (CH), 122.4 (CH), 124.4 (CH), 126.8 (CH), 129.2 (CH),
130.1 (C), 131.3 (C), 136.1 (C), 157.3 (C) ppm; IR (ATR) 2963,
2914, 1600, 1587, 1491, 1462, 1239 cm−1; MS (EI) m/z (%):
244 (M+, 34), 175 (M+ − C5H9, 100); HRMS (EI) m/z: calcd for
C17H24O (M+) 244.1822, found 244.1830.
(6E,9E)-2,6-Dimethylpentadeca-2,6,9-triene (7g)
Following the general procedure, 7g was obtained as colorless
oil (26.5 mg, 0.113 mmol, 89%, 9E/9Z 84 : 16).1H NMR
(300 MHz, CDCl3) δ 0.89 (t, J = 6.8 Hz, 3H), 1.25–1.40 (m,
6H), 1.61 (s, 6H), 1.69 (s, 3H), 1.95–2.13 (m, 6H), 2.70 (t, J =
5.8 Hz, 2H), 5.09–5.18 (m, 2H), 5.32–5.48 (m, 2H) ppm; 13C
NMR (75 MHz, CDCl3) δ 14.0 (CH3), 15.9 (CH2), 17.7 (CH3),
22.6 (CH2), 25.7 (CH3), 26.7 (CH2), 29.3 (CH2), 31.1 (CH2),
31.4 (CH2), 32.6 (CH2), 39.7 (CH2), 122.5 (CH), 124.3 (CH),
128.6 (CH), 130.4 (CH), 131.3 (C), 135.6 (C) ppm; IR (ATR)
2959, 2923, 2872, 2855, 1450, 1377 cm−1; MS (EI) m/z (%):
1692 | Org. Biomol. Chem., 2012, 10, 1686–1694
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234 (M+, 68), 219 (M+ − CH3, 34), 191 (M+ − C3H7, 87);
HRMS (EI) m/z: calcd for C17H30 (M+), 234.2342, found
234.2339.
lit. [α]2D0 −39.3 (c 2.51, CHCl3); HPLC (Chiralcel OD-H,
hexanes, 0.5 mL min−1): tr(R) = 24.5 min, tr(S) = 25.4 min.
Acknowledgements
(1E,4E)-(5,9-Dimethyldeca-1,4,8-trienyl)benzene (7h)32
We are grateful to the Xunta de Galicia (INCITE08P-
Following the general procedure, 7h was obtained as colorless
oil (15.4 mg, 0.064 mmol, 54%, 1E/1Z 92 : 8).1H NMR
(300 MHz, CDCl3) δ 1.63 (s, 3H), 1.68 (s, 3H), 1.71 (s, 3H),
2.02–2.14 (m, 4H), 2.93 (t, J = 6.8 Hz, 2H), 5.11–5.17 (m, 1H),
5.22–5.28 (m, 1H), 6.17–6.26 (dt, J = 6.3, 15.8 Hz, 1H), 6.40
(d, J = 15.8 Hz, 1H), 7.17–7.38 (m, 5H) ppm; 13C NMR
(75 MHz, CDCl3) δ 16.1 (CH3), 17,7 (CH3), 25.7 (CH3), 26.7
(CH2), 31.5 (CH2), 39.7 (CH2), 121.4 (CH), 124.3 (CH), 125.9
(2 × CH), 126.8 (CH), 128.4 (2 × CH), 129.5 (2 × CH), 131.5
(C), 136.7 (C), 137.9 (C) ppm; IR (ATR) 2962, 2922, 2853,
1493, 1446, 1376 cm−1; MS (EI) m/z (%): 240 (M+, 10), 171
(M+ − C5H9, 14), 91 (100); HRMS (EI) m/z: calcd for C18H24
(M+) 240.1873, found 240.1875.
XIB103167PR) and Ministerio de Ciencia
e Innovación
(CTQ2009-07180) for financial support. M.P.L. thanks Minis-
terio de Ciencia e Innovación for an FPU predoctoral fellowship.
Notes and references
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(R)-(E)-4-Phenyl-3-buten-2-ol17
1H NMR (300 MHz, CDCl3) δ 1.39 (d, J = 6.4 Hz, 3H), 4.51
(quint, J = 6.3 Hz, 1H), 6.28 (dd, J = 6.1, 15.9 Hz, 1H), 6.58 (d,
J = 16.0 Hz, 1H), 7.22–7.41 (m, 5H) ppm; 13C NMR (75 MHz,
CDCl3) δ 23.4 (CH3), 68.9 (CH), 126.4 (2 × CH), 127.6 (CH),
128.6 (2 × CH), 129.4 (CH), 133.5 (CH), 136.7 (C) ppm; IR
(ATR) 3356, 3026, 2972, 2925, 1403, 1448 cm−1; MS (EI) m/z
(%): 148 (M+, 85), 133 (M+ − CH3, 34), 105 (100); HRMS (EI)
m/z: calcd for C10H12O (M+) 148.0883, found 148.0878; [α]2D0
+33.2 (c 0.55, CHCl3), lit. [α]2D0 = +31.4 (c 1.38, CHCl3).
=
(R)-(E)-4-Phenyl-3-buten-2-yl acetate ((R)-(E)-8)33
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1H NMR (300 MHz, CDCl3) δ 1.42 (d, J = 6.5 Hz, 3H), 2.09 (s,
3H), 5.49–5.59 (m, 1H), 6.20 (dd, J = 6.7, 16.0 Hz, 1H), 6.61
(d, J = 16.0 Hz, 1H), 7.22–7.41 (m, 5H) ppm; 13C NMR
(75 MHz, CDCl3) δ 20.4 (CH3), 21.4 (CH3), 71.0 (CH), 126.5
(2 × CH), 127.9 (CH), 128.6 (2 × CH), 128.8 (CH), 131.5 (CH),
136.3 (C), 170.3 (C) ppm; IR (ATR) 3027, 2980, 2931,
1731 cm−1; MS (EI) m/z (%): 190 (M+, 13), 148 (100), 147 (M+
− C2H3O, 68); HRMS (EI) m/z: calcd for C12H14O2 (M+)
190.0988, found 190.0993; [α]2D0 = +148.7 (c 0.64, CHCl3), lit.
[α]2D0 = +142.2 (c 1.0, CHCl3); HPLC (Chiralcel OD-H, hexanes,
1.0 mL min−1): tr(R) = 35.4 min, tr(S) = 50.4 min.
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(S)-(E)-1,3-Diphenyl-1-butene ((S)-(E)-9)34
Following the general procedure, (S)-(E)-9 was obtained as col-
orless oil (29.0 mg, 0.139 mmol, 83%, >99% ee).1H NMR
(300 MHz, CDCl3) δ 1.50 (d, J = 6.9 Hz, 3H), 3.63–3.72 (m,
1H), 6.42–6.44 (m, 2H), 7.19–7.40 (m, 10H) ppm; 13C NMR
(75 MHz, CDCl3) δ 21.2 (CH3), 42.6 (CH), 126.1 (2 × CH),
126.2 (CH), 127.0 (CH), 127.3 (2 × CH), 128.5 (4 × CH), 128.6
(CH), 135.3 (CH), 137.6 (C), 145.6 (C) ppm; IR (ATR) 3027,
2961, 2924, 2853, 1602, 1494 cm−1; MS (EI) m/z (%): 208 (M+,
100), 193 (M+ − CH3, 89); HRMS (EI) m/z: calcd for C16H16
(M+) 208.1247, found 208.1246; [α]D20 −31.4 (c 2.50, CHCl3),
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ESI.
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