An efficient and practical synthesis of BINAM derivatives by diastereoselective [3,3]-rearrangement

Article abstract of DOI:10.1016/j.tetasy.2014.06.006

This work describes an efficient, practical, and diastereoselective synthesis of enantiomerically pure BINAM derivatives by utilizing the acid-catalyzed [3,3]-sigmatropic rearrangement of readily accessible N-(-)-menthoxycarbonyl-diaryl hydrazines as a key step. The yield of the rearrangement is very high and two diastereomers thus obtained are easily separable.

Full text of DOI:10.1016/j.tetasy.2014.06.006

Tetrahedron: Asymmetry 25 (2014) 1002–1007
Contents lists available at ScienceDirect
Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
An efficient and practical synthesis of BINAM derivatives
by diastereoselective [3,3]-rearrangement
⇑
⇑
Bing Li, Shengyong Zhang , Weiping Chen
School of Pharmacy, Fourth Military Medical University, 169 Changle West Road, Xi’an 710032, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 April 2014
Accepted 7 June 2014
This work describes an efficient, practical, and diastereoselective synthesis of enantiomerically pure
BINAM derivatives by utilizing the acid-catalyzed [3,3]-sigmatropic rearrangement of readily accessible
N-(ꢀ)-menthoxycarbonyl-diaryl hydrazines as a key step. The yield of the rearrangement is very high and
two diastereomers thus obtained are easily separable.
Ó 2014 Elsevier Ltd. All rights reserved.
1
. Introduction
of diaryl hydrazines may potentially be a powerful and general
approach to either racemic or optically active BINAM deriva-
1
0,11
Over the past three decades, axially chiral biaryls, a ‘privileged
tives.
Indeed, recently, Kürti et al. and List et al. developed
scaffold’ for the construction of effective chiral ligands and cata-
lysts, have played a key role in the development of catalytic asym-
metric catalysis.1 Arguably, axially chiral biaryls are one of the
independently the highly enantioselective synthesis of biaryl
amines using a chiral phosphoric acid catalyzed [3,3]-rearrange-
ment. Unfortunately, this methodology, from a practical view,
12
most successful classes of ligands and catalysts, and various C
and C -symmetrical biaryls (e.g., BINAP, BINOL, and their deriva-
1
is limited by the difficult accessibility of the starting diaryl hydra-
1
2,13
2
zines and chiral phosphoric acids.
A stereoselective, conve-
tives) differing in the steric and electronic properties have been
developed and applied in a wide range of catalytic enantioselective
processes, including several cases on industrial scales.2 Currently,
biaryl-type chiral ligands and catalysts are primarily prepared by
nient, and powerful synthetic approach to structurally diverse
BINAM derivatives will have a profound impact on the discovery
of new biaryl-type chiral ligands and catalysts. Herein, we report
an efficient and practical synthesis of BINAM derivatives by diaste-
reoselective [3,3]-rearrangement.
2
Cu(II), Fe(III), Mn(III), or V(IV)/O mediated oxidative couplings of
arenols,3 to afford the corresponding biaryl diols, which are con-
Recently, Cho et al. reported on an efficient synthesis of racemic
BINAM derivatives by acid-catalyzed [3,3]-rearrangement of
0
verted into other analogs including BINAP and 1,1 -binaphthyl-
0
14
2
,2 -diamine (BINAM) derivatives.
N-Cbz- or Boc-diaryl hydrazines. We envisioned that replacing
BINAM derivatives are highly useful chiral biaryls, and several
the Cbz and Boc groups in the N-Cbz- and Boc-diaryl hydrazines
with an easily available chiral alkoxycarbonyl would make the
rearrangement diastereoselective, and the resulting two diastereo-
mers could be readily separable, thus providing an efficient, prac-
tical, and diastereoselective [3,3]-rearrangement approach to
BINAM derivatives (Scheme 1).
well-established BINAM-based catalysts have been developed for
asymmetric catalysis.4 However, the lack of general synthetic
methods hampers their exploitation to their full potential. Stereo-
selective attempts toward enantiopure BINAM derivatives are rare
,5
6
and their preparation mainly relies on classical resolution,
although a moderately enantioselective oxidative homocoupling
7
of 2-naphthylamines has been reported. Unlike the BINOL system,
2
. Results and discussion
an oxidative coupling approach is not effective and gives only lim-
8
ited success. Very recently, Tan et al. reported on a highly efficient
Readily available and inexpensive (1R,2S,5R)-(ꢀ)-menthol was
strategy for the kinetic resolution of BINAM derivatives involving a
chiral Brønsted acid-catalyzed imine formation and transfer hydro-
genation cascade process.9 An acid-catalyzed [3,3]-rearrangement
utilized as a chiral auxiliary, and N-(ꢀ)-menthoxycarbonyl-diaryl
hydrazines 5a and 5b were easily prepared (Scheme 2). Following
the literature procedure, the reaction of (ꢀ)-menthol with triphos-
gene in toluene, in the presence of pyridine, gave quantitatively
1
5
(
ꢀ)-menthyl chloroformate 2, which was in turn treated with
⇑
Corresponding authors. Tel.: +86 02984776775 (W.C.).
E-mail address: wpchen@fmmu.edu.cn (W. Chen).
excess hydrazine hydrate to afford (ꢀ)-menthyl carbazate 3 in
http://dx.doi.org/10.1016/j.tetasy.2014.06.006
957-4166/Ó 2014 Elsevier Ltd. All rights reserved.
0

B. Li et al. / Tetrahedron: Asymmetry 25 (2014) 1002–1007
1003
A. Known methods:
bonyl-diaryl hydrazines 5a and 5b were obtained in 70% and 60%
yield respectively by the t-Bu P/Pd(OAc) catalyzed coupling reac-
3
2
14
R1
R1
tion of N-aryl-(ꢀ)-menthyl carbazate 4 with 2-naphthyl bromide.
HA
With the biaryl hydrazine precursor 5a in hand, the [3.3]-
sigmatropic rearrangement conditions were screened (Table 1).
Thus, after a solution of 5a and concentrated hydrochloric acid
NH
NH
or HA*
NH2
NH2
R2
R2
(
12 equiv) in EtOH was refluxed for 20 min, the rearrangement
reaction was completed to afford the desired diastereomeric prod-
ucts 6a (43%) and 7a (37%) along with the carbazole by-product 8a
racemic or
optically active
diaryl hydrazines
(
20%) (entry 1). The absolute configuration (axial chirality) of 6a
0
was assigned as (R
thyl-2,2 -diamine by hydrolysis (vide infra). Lowering the reaction
temperature to rt had no significant effect on the diastereo- or
a
) after it was converted into (R
a
)-1,1 -binaph-
R1
R1
0
NX
NH
HA
NHX
NH2
3
chemoselectivity (entry 2). Using CHCl as the solvent improved
both the diastereo- and chemoselectivity (entries 3 and 4). Since
chloroform appeared to be a better solvent than ethanol, a variety
R2
R2
of acids were screened by using CHCl
3
as the solvent (entries
X = Cbz or Boc
B. Herein:
racemic
5
–10). Trifluoroacetic acid gave the highest chemoselectivity
(entry 6) and (1R)-(ꢀ)-10-camphorsulfonic acid afforded the
R1
highest diastereoselectivity (entry 10). Obviously, the chirality of
(
1R)-(ꢀ)-10-camphorsulfonic acid is matched for the formation
NHCO2R*
NH2
0
0
a
of (R )-1,1 -binaphthyl-2,2 -diamine derivative 6a, while (1S)-
(
+)-10-camphorsulfonic acid is the mismatched one, although the
R2
R1
difference in product distribution of the matched case and
mismatched case was not significant. Weaker organic acids, such
as acetic acid and formic acid, were unable to catalyze this rear-
rangement (entries 7 and 8). Lowering the reaction temperature
from 25 °C to ꢀ15 °C had no influence on either the diastereo- or
chemoselectivity (entries 4 vs 11 and entries 10 vs 12).
NCO2R* acid
NH
+
R2
R1
NHCO2R*
NH2
Considering both the diastereo- and chemoselectivity, we uti-
R2
3
lized concentrated hydrochloric acid (12 equiv) and CHCl as the
solvent for 12 h at room temperature as the reaction conditions
in the practical synthesis of BINAM derivatives (Scheme 3). Thus,
in the presence of 12 equiv of concentrated hydrochloric acid, a
R* = (1R,2S,5R)-(-)-menthyl
diastereoselective and readily separable
3
solution of 5a in CHCl was stirred for 12 h at room temperature
to give a mixture of the two diastereomers 6a and 7a along with
a small amount of carbazole by-product 8a. The two diastereomers
Scheme 1. An efficient and practical approach to BINAM derivatives utilizing a
diastereoselective [3,3]-rearrangement.
6
a and 7a were easily separated by column chromatography on sil-
ica gel, giving 53% of 6a and 39% of 7a. Similarly, 6b and 7b were
obtained in 47% and 44% yield, respectively.
H
Finally, pure diastereomers 6 and 7 were hydrolyzed to afford
free BINAM 9 (Scheme 4). The hydrolysis could be catalyzed either
by acid or base. In accordance with Cho’s observation,18 under
acidic conditions, BINAM undergoes ring-closure condensation to
afford benzo[c]carbazole by-products 8. Thus, a mixture of 6a
and concentrated hydrochloric acid in acetic acid was refluxed
for 24 h to give (R)-9a in 94% yield along with 5% of benzo[c]carba-
zole by-product 8a. Fortunately, the side reaction of benzo[c]carba-
zole formation was not observed in the base-catalyzed hydrolysis.
A mixture of 6a and 40% KOH aqueous solution in EtOH was
refluxed for 12 h to afford (R)-9a in 97% yield. Similarly, (R)-9b
was obtained from 6b, (S)-9a and (S)-9b from 7a and 7b, respec-
tively. The enantiomeric purities of products (R)-9a, (R)-9b, (S)-
9a, and (S)-9b thus obtained were determined by chiral HPLC to
be >99% ee.
HO
Cl
O
N
O
a
b
H N
2
O
O
1
2
3
NH2
N
O
NH
c
d
NCO2(-)-Men
O
X
X
4
4
a: X = H, 60%
b: X = MeO, 80%
5a: X = H, 70%
b: X = MeO, 60%
5
Scheme 2. Synthesis of N-(ꢀ)-menthoxycarbonyl-diaryl hydrazines. Reagents and
conditions: (a) Triphosgene, pyridine, toluene, ꢀ10 °C, 100%; (b) 80% NH NH ꢁH O,
triethylbenzylamonium chloride, K CO , CCl -CH Cl , rt, 85%; (c) aryl bromide, CuI,
-hydroxy- -proline, DMSO, 80 °C, 75%; (d) 2-naphthyl bromide, Pd(OAc) , (t-Bu) P,
Cs CO , toluene, reflux.
2
2
2
2
3
4
2
2
3
. Conclusion
4
L
2
3
2
3
In conclusion, an efficient, practical, and diastereoselective syn-
thesis of enantiomerically pure BINAM derivatives has been devel-
oped by the acid-catalyzed [3,3]-rearrangement of the readily
accessible N-(ꢀ)-menthoxycarbonyl-diaryl hydrazines. The yield
of the rearrangement is very high and the two diastereomers thus
obtained are easily separable.
1
6
8
5% yield. The CuI/4-hydroxy-
L
-proline-catalyzed coupling reac-
tion of 2-naphthyl and 6-methoxy-2-naphthyl bromides with
ꢀ)-menthyl carbazate 3 furnished N-aryl-(ꢀ)-menthyl carbazate
a and 4b in 60% and 80% yield, respectively. N-(ꢀ)-Menthoxycar-
1
7
(
4

1
004
B. Li et al. / Tetrahedron: Asymmetry 25 (2014) 1002–1007
Table 1
0
a
[
3,3]-Rearrangement of N-(ꢀ)-menthoxycarbonyl-N,N -di(2-naphthyl)hydrazine 5a
NCO2Men
NH
NHCO Men
NHCO Men
acid
2
2
NH
+
+
NH2
NH2
5a
8a
6
a
7a
Entry
Acid
Solvent
Temp (°C)
6a:7a:8ab,c
1d
2
3
HCl
HCl
HCl
HCl
p-TsOH
TFA
Acetic acid
Formic acid
(1S)-(+)-CSA
(1R)-(ꢀ)-CSA
HCl
EtOH
EtOH
Reflux
rt
Reflux
rt
43.2:36.8:20.0
44.8:35.2:20.0
54.1:39.2:6.7
55.1:38.3:6.6
53.6:37.3:9.1
50.0:44.4:5.6
N. R.
d
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
3
3
3
3
3
3
3
3
3
3
4
5
6
rt
rt
rt
rt
rt
rt
e
7
e
8
N. R.
9
48.3:35.0:16.7
56.4:30.3:13.3
55.1:38.3:6.6
50.3:36.4:13.3
10
11
12
f
f
ꢀ15
(1R)-(ꢀ)-CSA
ꢀ15
a
Reactions were carried out in solvent (3 mL), 5a (0.15 mmol), and acid (12 equiv) at room temperature for 12 h, and the total yields of 6a, 7a, and 8a are essentially
quantitative unless otherwise specified.
b
Determined by HPLC and 1H NMR spectroscopy.
The absolute configuration (axial chirality) of 6a was assigned as (R
Reacted for 20 min.
No reaction.
c
0
0
a
) after it was converted into (R
a
)-1,1 -binaphthyl-2,2 -diamine by hydrolysis.
d
e
f
Reacted for 24 h.
conc. HCl
NH
(12 equiv.)
NH2
NH2
+
+
NCO2Men
CHCl3
NH
NHCO2Men
NHCO2Men
rt, 12 h
X
X
X
X
5
5
a: X = H
6a: X = H, 53%
7a: X = H, 39%
8a: X = H, trace
b: X = MeO
6b: X = MeO, 47%
7b: X = MeO, 44%
8b: X = MeO, trace
Scheme 3. Synthesis of BINAM derivatives by acid-catalyzed [3,3]-rearrangement.
4
4
. Experimental
Stirring was continued for 15 min at 0 °C and a solution of
(
ꢀ)-menthol 1 (28.12 g, 0.18 mol) in toluene (100 mL) was then
.1. General
added slowly through a dropping funnel. The reaction mixture
was allowed to warm to rt and stirred for 15 h. The reaction
mixture was then diluted with water (300 mL) and extracted with
toluene (2 ꢂ 200 mL). The combined organic layers were washed
sequentially with water (200 mL) and brine (200 mL) and dried
The H and 13C NMR spectra were recorded on a Bruker AV-400
1
spectrometer using TMS as an internal reference. Coupling con-
stant (J) values are given in Hz. Melting points were obtained on
a Micro Melting Point Instrument (XRC-1) that was uncalibrated.
Optical rotation analyses were performed on a Perkin-Elmer Model
(Na
2
SO
4
). The solvent was removed in vacuo to give (ꢀ)-menthyl
chloroformate 2 as a colorless oil (39.3 g), which was used directly
in the next step without further purification.
3
43 Polarimeter. HRMS were recorded on a ZAB-HS spectrometer
with ES ionization (ESI). All commercially available reagents were
used as received. Solvents and reagents were purified and dried
by standard methods prior to use. Products were purified by flash
column chromatography on silica gel purchased from Qingdao
Haiyang Chemical Co., Ltd. All reactions involving air or moisture
sensitive species were performed under an inert atmosphere in
oven-dried glassware.
To a stirred solution of benzyltriethylammonium chloride
(0.02 g, 0.1 mmol) and K
and CH Cl (40 mL), was added hydrazine hydrate 80% (2.0 g,
50 mmol) at rt. After 15 min at room temperature, a solution of
(ꢀ)-menthyl chloroformate (2.19 g, 10 mmol) in CH Cl
(10 mL), was added dropwise. Next, the mixture was stirred at rt
for 3 h. The crude mixture was washed with H
O (2 ꢂ 20 mL) and
extracted with CH Cl (10 mL), and the solvent was dried over
MgSO and evaporated under vacuum. The crude product was
2 3 4
CO (2.07 g, 15 mmol) in CCl (10 mL)
2
2
2
2
2
2
2
2
4
.2. Synthesis of (ꢀ)-menthyl carbazate 3
4
purified by crystallization from hexanes to give (ꢀ)-menthyl
A solution of pyridine (21.9 mL, 0.27 mol) in toluene (150 mL)
carbazate (1.81 g, 85% over 2 steps) as a white solid. White solid
1
was added dropwise to a stirred solution of triphosgene (21.96 g,
.074 mol) in toluene (260 mL) at 0 °C under an argon atmosphere.
(1.81 g, 85%); H NMR (400 MHz, CDCl
3
) d 5.93 (s, 1H), 4.59 (td,
0
J = 10.9, 4.4 Hz, 1H), 3.74 (d, J = 3.7 Hz, 2H), 2.04 (dd, J = 7.3,

B. Li et al. / Tetrahedron: Asymmetry 25 (2014) 1002–1007
1005
NH2
conc. HCl
NH2
NH2
NH
NHCO (-)-Men
+
2
AcOH
refl. 24 h
6
a
(
R)-9a
4%
8a
9
5%
NH2
NH2
NH2
4
0% KOH
EtOH
NHCO2(-)-Men
Refl.12 h
X
X
6a: X = H
(R)-9a: X = H, 97%
6b: X = MeO
(R)-9b: X = MeO, 98%
NH2
NH2
NH2
4
0% KOH
NHCO2(-)-Men
EtOH
Refl.12 h
X
X
7a: X = H
(S)-9a: X = H, 97%, >99% ee
7b: X = MeO
(S)-9b: X = MeO, 96%, >99% ee
Scheme 4. Synthesis of enantiomerically pure free BINAM derivatives.
4
6
.6 Hz, 1H), 1.90 (dtd, J = 13.9, 7.0, 2.6 Hz, 1H), 1.67 (ddd, J = 9.2,
.4, 3.2 Hz, 2H), 1.49 (ttd, J = 12.8, 6.5, 3.3 Hz, 1H), 1.33 (t,
1H), 1.34 (t, J = 11.4 Hz, 1H), 1.17–0.66 (m, 13H); 13C NMR
(101 MHz, CDCl ): d 157.5, 132.2, 129.2, 128.6, 126.7, 123.7,
121.4, 119.0, 105.5, 55.3, 47.1, 41.3, 34.1, 31.4, 26.3, 23.4, 22.0,
3
J = 11.4 Hz, 1H), 1.24–0.71 (m, 13H).
+
2
0.8, 16.4; HRMS (ESI) calcd for C22
30 2 3
H N O [M+Na] : 393.2154;
4
.3. General procedure for the preparation of 4
found: 393.2149.
A mixture of aryl bromide (0.24 mmol), (ꢀ)-menthyl carbazate
4.4. General procedure for the preparation of 5
(
2 3
103 mg, 0.48 mmol), Cs CO (156 mg, 0.48 mmol), CuI (4.6 mg,
0
.024 mmol), and 4-hydroxy-
L
-proline (6.3 mg, 0.048 mmol) in
A mixture of 4 (1.29 mmol), 2-bromonaphthalene (222 mg,
0
.25 mL of DMSO was heated at 80 °C until bromide was consumed
1.07 mmol), Pd(OAc)
2
(12 mg, 5 mol %), P(t-Bu)
3
(15.5 mg,
as indicated by TLC. The cooled mixture was partitioned between
water and ethyl acetate. The organic layer was separated, and the
aqueous layer was extracted with ethyl acetate. The combined
5 mol %), Cs CO (523 mg, 1.6 mmol), and 10 mL of anhydrous tol-
2
3
uene was heated at 110 °C for 1.5–3 h. The reaction mixture was
cooled, concentrated, and chromatographed to afford the corre-
sponding 5.
2 4
organic layers were washed with brine, dried over Na SO , and
concentrated in vacuo to give an oil, which was purified by flash
chromatography on silica gel.
0
4.4.1. N,N -Di(2-naphthyl)hydrazinecarboxylic acid (ꢀ)-menthyl
ester 5a
2
5
4
4
.3.1. N-(2-Naphthyl)hydrazinecarboxylic acid (ꢀ)-menthyl ester
White solid (349 mg, 70%); mp 140–141 °C; [
a]
D
= ꢀ78.9 (c 1,
1
a
CH Cl ); H NMR (400 MHz, CDCl ): d 8.15 (s, 1H), 7.96–7.68 (m,
2
2
3
25
); 1H NMR
Yellow oil (72 mg, 60%); [
a]
D
= ꢀ42.1 (c 1, CH
2
Cl
2
6H), 7.61 (d, J = 8.2 Hz, 1H), 7.41 (ddd, J = 21.6, 14.4, 7.1 Hz, 3H),
7.29 (d, J = 7.6 Hz, 1H), 7.14 (s, 1H), 7.08 (dd, J = 8.8, 2.0 Hz, 1H),
6.65 (s, 1H), 4.62 (td, J = 10.7, 3.8 Hz, 1H), 2.10 (d, J = 10.0 Hz,
1H), 1.51 (ddd, J = 31.6, 12.9, 8.1 Hz, 3H), 1.16 (t, J = 10.7 Hz, 1H),
1.05–0.66 (m, 7H), 0.46 (s, 6H); C NMR (101 MHz, CDCl ):
3
d 154.9, 145.7, 140.1, 134.4, 133.5, 130.8, 129.4, 129.3, 128.3,
127.8, 127.6, 127.4, 126.6, 126.5, 126.2, 125.2, 123.5, 120.9,
115.4, 107.3, 46.9, 41.0, 34.0, 31.3, 25.2, 22.8, 21.9, 20.4, 15.6;
HRMS (ESI) calcd for C31
467.2695.
(
400 MHz, CDCl ): d 7.90 (s, 1H), 7.79 (dd, J = 8.4, 4.3 Hz, 3H),
3
7
4
4
4
.65 (d, J = 8.7 Hz, 1H), 7.51–7.38 (m, 2H), 4.72 (td, J = 10.9,
.4 Hz, 1H), 4.60 (s, 2H), 2.15 (d, J = 12.0 Hz, 1H), 1.94 (dq, J = 6.9,
.5 Hz, 1H), 1.67 (d, J = 10.4 Hz, 2H), 1.51 (ddd, J = 11.8, 8.9,
1
3
1
3
.4 Hz, 1H), 1.36 (t, J = 11.6 Hz, 1H), 1.10–0.69 (m, 13H); C NMR
): d 156.1, 140.3, 133.3, 131.0, 128.9, 127.9,
27.8, 127.5, 126.2, 125.4, 123.0, 120.9, 47.1, 41.3, 34.1, 31.4,
6.4, 23.4, 22.0, 20.8, 16.4; HRMS (ESI) calcd for C21
(
101 MHz, CDCl
3
1
2
+
28
H N
2
O
2
H
34
N
2
O
2
[M+H] : 467.2699; found:
+
[
M+H] : 341.2229; found: 341.2226.
0
4
.3.2. N-(6-Methoxy-2-naphthyl)hydrazinecarboxylic acid (ꢀ)-
4.4.2. N -(6-Methoxy-2-naphthyl)-N-(2-naphthyl)hydrazinecar-
menthyl ester 4b
boxylic acid (ꢀ)-menthyl ester 5b
25
); 1H NMR
25
Yellow oil (71 mg, 80%); [
a]
D
= ꢀ43.2 (c 1, CH
2
Cl
2
Yellow solid (298 mg, 60%); mp 66.5–67.5 °C; [
a]
D
= ꢀ42.1 (c
1
(
7
1
400 MHz, CDCl
3
): d 7.79 (s, 1H), 7.68 (dd, J = 8.6, 2.6 Hz, 2H),
.57 (d, J = 8.7 Hz, 1H), 7.21–7.07 (m, 2H), 4.68 (tt, J = 35.5,
7.7 Hz, 3H), 3.91 (s, 3H), 2.14 (d, J = 11.8 Hz, 1H), 1.93 (dd,
2 2 3
0.5, CH Cl ); H NMR (400 MHz, CDCl ): d 8.15 (s, 1H), 7.88 (d,
J = 8.9 Hz, 1H), 7.85–7.75 (m, 3H), 7.64 (d, J = 8.7 Hz, 1H), 7.56–
7.49 (m, 1H), 7.49–7.37 (m, 2H), 7.15–7.01 (m, 4H), 6.59 (s, 1H),
4.62 (td, J = 10.8, 4.0 Hz, 1H), 3.88 (s, 4H), 2.10 (d, J = 10.9 Hz,
J = 13.6, 5.6 Hz, 1H), 1.65 (dd, J = 12.8, 7.3 Hz, 2H), 1.58–1.42 (m,

1
006
B. Li et al. / Tetrahedron: Asymmetry 25 (2014) 1002–1007
1
0
1
1
5
1
H), 1.57 (ddd, J = 27.7, 13.2, 2.6 Hz, 3H), 1.31–1.12 (m, 2H), 0.93–
29.7, 26.9, 26.4, 23.7, 21.9, 20.6, 16.7, 14.1, 11.4; HRMS (ESI) calcd
for C32H N O [M+H] : 497.2804; found: 497.2797.
36 2 3
.79 (m, 7H), 0.47 (s, 5H); 13C NMR (101 MHz, CDCl
) d 156.0,
+
3
55.0, 144.1, 140.3, 133.5, 130.8, 130.3, 129.8, 128.2, 128.1,
27.8, 127.4, 126.2, 125.2, 121.0, 119.1, 115.9, 107.9, 105.9, 71.5,
0
4.5.5. (1R,2S,5R)-2-Isopropyl-5-methylcyclohexyl [(R)-2 -amino-
0
5.2, 50.1, 46.9, 45.0, 41.1, 34.5, 34.0, 31.3, 25.8, 22.9, 21.9, 20.5,
6-methoxy-1,1 -binaphthalen]-2-yl] carbamate (R
a
)-(+)-6b
+
25
6.1, 15.6; HRMS (ESI) calcd for C32
H
36
N
2
O
3
[M+H] : 497.2804;
Light yellow solid (66 mg, 44%); mp 59.2–60.2 °C; [
a]
D
= +26.1
): d 8.43 (d, J = 8.9 Hz,
H), 7.98 (d, J = 9.1 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.76 (d,
J = 8.8 Hz, 1H), 7.39 (t, J = 7.4 Hz, 1H), 7.28 (d, J = 8.3 Hz, 2H), 7.16
dd, J = 19.0, 9.0 Hz, 3H), 6.96–6.82 (m, 2H), 6.38 (s, 1H), 4.54 (td,
1
found: 497.2794.
2 2 3
(c 0.25, CH Cl ); H NMR (400 MHz, CDCl
1
4
.5. General procedure for the preparation of 6 and 7
(
A mixture of 5 (0.3 mmol), 6 mL of CHCl
35%, 374 mg, 3.6 mmol) was stirred at room temperature for 12 h,
and then neutralized with an NaHCO saturated solution. The
crude mixture was washed with H
O (2 ꢂ 20 mL) and extracted
with CH Cl (20 mL), and the solvent was dried over MgSO and
3
, and concentrated HCl
J = 10.9, 4.2 Hz, 1H), 3.88 (s, 3H), 3.54 (s, 2H), 2.00 (d, J = 11.7 Hz,
1H), 1.61 (d, J = 15.2 Hz, 2H), 1.44 (d, J = 8.4 Hz, 2H), 1.12 (d,
J = 11.8 Hz, 1H), 0.91–0.84 (m, 6H), 0.64 (dd, J = 32.6, 6.9 Hz, 6H);
C NMR (101 MHz, CDCl ): d 155.5, 153.8, 141.0, 135.1, 132.3,
3
130.7, 129.2, 129.1, 128.9, 128.8, 128.2, 126.8, 125.2, 125.1,
124.7, 120.0, 119.4, 118.7, 111.3, 106.7, 75.0, 55.2, 47.0, 41.2,
(
3
1
3
2
2
2
4
evaporated under vacuum. The residue was subjected to chroma-
tography to afford pure diastereomers 7 and 6.
34.2, 31.3, 29.7, 29.3, 26.0, 23.6, 22.7, 22.0, 20.3, 16.4, 14.1; HRMS
+
(
ESI) calcd for C32
H
36
N
2
O
3
[M+H] : 497.2804; found: 497.2796.
0
4
1
.5.1. (1R,2S,5R)-(2-Isopropyl-5-methylcyclohexyl) [(S)-2 -amino-
0
,1 -binaphthalen-2-yl] carbamate (S
a
)-(ꢀ)-7a
4.6. General procedure for the preparation of (R)-(+)-9 and (S)-
(ꢀ)-9
2
5
Light yellow solid (74 mg, 53%); mp 192.1–193.1 °C; [
a]
D
=
1
ꢀ
2 2 3
58.3 (c 0.5, CH Cl ); H NMR (400 MHz, CDCl ): d 8.43 (d,
J = 8.9 Hz, 1H), 7.99 (d, J = 9.1 Hz, 1H), 7.93–7.76 (m, 3H), 7.39 (t,
J = 7.4 Hz, 1H), 7.18 (ddd, J = 22.5, 19.2, 11.5 Hz, 5H), 6.92 (d,
J = 8.3 Hz, 1H), 6.41 (s, 1H), 4.57 (td, J = 10.8, 4.2 Hz, 1H), 3.65 (s,
A mixture of 6 or 7 (70 mg, 0.15 mmol), 3 mL of 40% KOH aque-
ous solution, and 6 mL of EtOH was heated at reflux for 12 h. The
mixture was partitioned between water and ethyl acetate. The
2
2
1
1
1
3
C
H), 1.95 (d, J = 10.9 Hz, 1H), 1.84–1.73 (m, 1H), 1.67–1.57 (m,
2 4
organic layer was separated, dried over Na SO , and concentrated
in vacuo. The residue was purified by chromatography on silica
gel to afford (R)-(+)-9 or (S)-(ꢀ)-9.
H), 1.44 (s, 1H), 1.28–1.18 (m, 1H), 1.02 (dd, J = 24.1, 11.5 Hz,
H), 0.89–0.72 (m, 11H); 13C NMR (101 MHz, CDCl
3
): d 153.9,
42.8, 135.1, 133.8, 132.5, 130.8, 130.2, 129.2, 128.1, 127.1,
26.8, 125.2, 124.7, 123.7, 122.5, 118.0, 110.4, 75.2, 46.9, 41.0,
0
0
4.6.1. (R)-(+)-1,1 -Binaphthyl-2,2 -diamine (R)-(+)-9a
2
5
= +156 (c 0.25, pyridine); 1
H
4.1, 31.3, 26.4, 23.7, 21.9, 20.5, 16.8; HRMS (ESI) calcd for
White solid (41 mg, 97%); [
NMR (400 MHz, DMSO) d 7.83–7.73 (m, 4H), 7.22 (d, J = 8.8 Hz,
H), 7.17–7.05 (m, 4H), 6.86–6.72 (m, 2H), 4.64 (s, 4H); >99% ee,
HPLC: Daicel Chiralpak AD-3, n-hexane/i-PrOH = 85/15, flow
a]
D
+
31
H
34
N
2
O
2
[M+H] : 467.2699; found: 467.2690.
2
0
4
.5.2. (1R,2S,5R)-(2-Isopropyl-5-methylcyclohexyl) [(R)-2 -amino-
0
1,1 -binaphthalen-2-yl] carbamate (R
a
)-(+)-6a
rate = 1.0 mL/min, UV = 240 nm, t
min (S).
R
R
= 15.45 min (R) and t = 49.75 -
25
Light yellow solid (54 mg, 39%); mp 79.2–80.2 °C; [
a]
D
= +38.8
1
(c 0.5, CH Cl ); H NMR (400 MHz, CDCl ) d 8.45 (d, J = 9.0 Hz, 1H),
2
2
3
0
0
7
7
.99 (d, J = 9.0 Hz, 1H), 7.92–7.76 (m, 3H), 7.39 (t, J = 7.4 Hz, 1H),
.20 (m, 5H), 6.94 (d, J = 8.3 Hz, 1H), 6.39 (s, 1H), 4.54 (td,
4.6.2. (R)-(+)-6-Methoxy-[1,1 ]binaphthalenyl-2,2 -diamine (R)-
(+)-9b
13
25
J = 10.8, 4.3 Hz, 1H), 3.65 (s, 2H); C NMR (101 MHz, CDCl
3
) d
Yellow solid (46 mg, 98%); [
>200 °C; H NMR (400 MHz, CDCl ) d 7.87–7.74 (m, 2H), 7.71 (d,
3
a]
D
2 2
= +61.0 (c 0.25, CH Cl ); mp
1
1
1
1
2
C
53.84, 142.85, 135.25, 133.61, 132.41, 130.82, 130.26, 129.25,
28.24, 128.21, 128.12, 127.21, 126.84, 125.20, 124.76, 123.59,
22.62, 120.09, 118.14, 110.49, 75.11, 46.99, 41.19, 34.20, 31.38,
J = 8.7 Hz, 1H), 7.29–7.18 (m, 3H), 7.18–7.11 (m, 2H), 7.10–7.04
(m, 1H), 7.01 (d, J = 9.2 Hz, 1H), 6.90 (dd, J = 9.2, 2.5 Hz, 1H), 3.89
1
3
9.71, 26.07, 23.63, 22.02, 20.47, 16.44; HRMS (ESI) calcd for
(d, J = 9.9 Hz, 3H), 3.65 (s, 3H); C NMR (101 MHz, CDCl
155.43, 142.65, 140.95, 133.70, 129.48, 129.31, 128.97, 128.43,
28.21, 128.14, 126.84, 125.69, 123.94, 122.42, 119.06, 118.98,
118.29, 113.40, 112.71, 106.80, 55.32; HRMS (ESI) calcd for
3
) d
+
31
H
34
N
2
O
2
[M+H] : 467.2699; found: 467.2693.
1
4
.5.3. 7H-Dibenzo[c,g]carbazole 8a
1
+
Colorless solid (7 mg, 5%); H NMR (400 MHz, CDCl
3
) d 9.21 (d,
C H
21 18
N
2
O [M+H] : 315.1497; found: 315.1484; >99% ee, HPLC:
Chiralpak AD-3, n-hexane/i-PrOH = 85/15, flow
= 51.75 -
J = 8.5 Hz, 2H), 8.74 (s, 1H), 8.04 (d, J = 8.0 Hz, 2H), 7.86 (d,
J = 8.7 Hz, 2H), 7.77–7.61 (m, 4H), 7.52 (t, J = 7.4 Hz, 2H).
Daicel
rate = 1.0 mL/min, UV = 240 nm, t
min (S).
R
= 23.72 min (R) and t
R
0
4
6
.5.4. (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl [(S)-2 -amino-
-methoxy-1,1 -binaphthalen]-2-yl] carbamate (S
0
0
0
a
)-(ꢀ)-7b
4.6.3. (S)-(ꢀ)-1,1 -Binaphthyl-2,2 -diamine (S)-(ꢀ)-9a
2
5
Light yellow solid (70 mg, 47%); mp 68.0–69.0 °C;
[
a]
D
= ꢀ156 (c 0.25, pyridine). Spectroscopic data are identical
2
5
1
[a
]
D
= ꢀ28.3 (c 0.25, CH
2
Cl
2
3
); H NMR (400 MHz, CDCl ): d 8.43
to the data of (R)-(+)-9a. >99% ee.
(
d, J = 8.9 Hz, 1H), 7.98 (d, J = 9.1 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H),
0
0
7
1
.75 (d, J = 8.8 Hz, 1H), 7.38 (t, J = 7.4 Hz, 1H), 7.25 (t, J = 7.3 Hz,
H), 7.21–7.09 (m, 3H), 6.87 (dt, J = 17.5, 5.8 Hz, 2H), 6.39 (d,
4.6.4. (S)-(ꢀ)-6-Methoxy-[1,1 ]binaphthalenyl-2,2 -diamine (S)-
(ꢀ)-9b
2
5
J = 12.0 Hz, 1H), 4.57 (td, J = 10.9, 4.3 Hz, 1H), 3.89 (s, 3H), 3.51 (s,
[
a]
D
= ꢀ61.0 (c 0.25, CH
2 2
Cl ). Spectroscopic data are identical to
the data of (R)-(+)-9b. >99% ee.
2
1
1
H), 1.95 (d, J = 12.1 Hz, 1H), 1.80 (ddd, J = 13.7, 6.8, 4.6 Hz, 1H),
.66–1.57 (m, 2H), 1.49–1.39 (m, 1H), 1.19 (s, 1H), 1.07–0.97 (m,
H), 0.85 (dd, J = 6.5, 5.3 Hz, 8H), 0.75 (d, J = 6.9 Hz, 4H);
): d 155.4, 153.9, 141.0, 135.1, 132.5, 130.1,
29.2, 129.0, 128.9, 128.1, 126.8, 125.4, 125.2, 124.7, 120.1,
19.3, 118.7, 111.2, 106.8, 75.2, 55.3, 46.9, 41.0, 34.1, 31.9, 31.3,
1
3
C
Acknowledgement
NMR (101 MHz, CDCl
1
1
3
We thank the National Natural Science Foundation of China
(21272271, 21172262) for financial support.

B. Li et al. / Tetrahedron: Asymmetry 25 (2014) 1002–1007
1007
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Ed. 2003, 42, 5458; (m) Takenaka, N.; Huang, Y.; Rawal, V. H. Tetrahedron 2002,
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4