Catalytic asymmetric synthesis of axially chiral 2-amino-1,1′-biaryl compounds by phase-transfer-catalyzed kinetic resolution and desymmetrization

Article abstract of DOI:10.1016/j.tet.2015.10.074

An efficient methodology for kinetic resolution of axially chiral 2-amino-1,1′-biaryl compounds as useful chiral building blocks was developed by means of binaphthyl-modified chiral quaternary ammonium salt-catalyzed N-allylations under phase-transfer con

Full text of DOI:10.1016/j.tet.2015.10.074

Tetrahedron xxx (2015) 1e9
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0
Catalytic asymmetric synthesis of axially chiral 2-amino-1,1 -biaryl
compounds by phase-transfer-catalyzed kinetic resolution and
desymmetrization
a
a
,
b
a
b,
*
Seiji Shirakawa , Xiangfei Wu , Shiyao Liu , Keiji Maruoka
a
Department of Environmental Science, Graduate School of Fisheries and Environmental Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki
52-8521, Japan
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
8
b
a r t i c l e i n f o
a b s t r a c t
0
Article history:
An efficient methodology for kinetic resolution of axially chiral 2-amino-1,1 -biaryl compounds as useful
chiral building blocks was developed by means of binaphthyl-modified chiral quaternary ammonium
salt-catalyzed N-allylations under phase-transfer conditions. The catalyst structure and reaction condi-
tions were carefully optimized to achieve the highly selective kinetic resolutions. Various types of 2-
Received 31 August 2015
Received in revised form 22 October 2015
Accepted 26 October 2015
Available online xxx
0
amino-1,1 -biaryls were submitted to the kinetic resolution under the phase-transfer conditions to re-
solve the enantiomers with high selectivities. The synthetic utility of this method could be extended to
the asymmetric desymmetrization of diamino biaryl compounds to obtain the corresponding axially
chiral biaryls with high enantioselectivities.
Keywords:
Axial chirality
Biaryls
Phase-transfer catalysis
Organocatalysis
Asymmetric synthesis
Ó 2015 Published by Elsevier Ltd.
1. Introduction
Axially chiral biaryl compounds are indispensable building
blocks in modern organic synthesis. A wide variety of chiral ligands
and catalysts were designed based on the biaryl scaffolds, and these
chiral ligands and catalysts were utilized for various catalytic
asymmetric transformations to produce important chiral com-
1
pounds in optically enriched form. Furthermore, axially chiral
biaryl skeletons are observed in the structure of biologically active
natural products.2 Thus, the development of efficient enantiose-
lective methods for the synthesis of axially chiral biaryls is an im-
3
portant task in the field of organic chemistry. Among the
enantioselective synthesis of axially chiral biaryls, we are interested
0
in the catalytic asymmetric synthesis of 2-amino-1,1 -biaryls, ow-
ing to their high synthetic utility as chiral building blocks for the
synthesis of important chiral ligands, catalysts, and biologically
4
,5
0
Fig. 1. Representative axially chiral 2-amino-1,1 -biaryls.
active compounds (Fig. 1). Herein, we report our approach for the
0
catalytic asymmetric synthesis of 2-amino-1,1 -biaryl com-
pounds6 via kinetic resolution and desymmetrization by chi-
,7
8,9
10
11,12
2. Results and discussion
ral phase-transfer-catalyzed N-allylations (Scheme 1).
We first investigated the effect of binaphthyl-modified chiral
quaternary ammonium salts 3e5 in the kinetic resolution of 2-
0
0
amino-2 -hydroxy-1,1 -binaphthyl (NOBIN) derivative (ꢀ)-1a, as
*
Corresponding author. Tel./fax: þ81 75 753 4041; e-mail address: maruoka@
4
a useful chiral building block, through N-allylation under the
kuchem.kyoto-u.ac.jp (K. Maruoka).
http://dx.doi.org/10.1016/j.tet.2015.10.074
0
040-4020/Ó 2015 Published by Elsevier Ltd.
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2
S. Shirakawa et al. / Tetrahedron xxx (2015) 1e9
Table 1
a
Effect of chiral phase-transfer catalysts
0
Scheme 1. Our approach for catalytic asymmetric synthesis of 2-amino-1,1 -biaryls.
phase-transfer conditions (Table 1). The reaction of (ꢀ)-1a pos-
sessing a benzenesulfonamide moiety with allyl iodide (0.75 equiv)
in aqueous KOH/toluene biphasic solution catalyzed by (S,S)-3a or
1
3
3
0
c, which were some of most reliable phase-transfer catalysts, at
ꢁ
C for 48 h afforded the allylation product 2a with low to mod-
erate selectivities (s¼1.6e6.4, entries 1 and 2). The simplified-type
14
catalysts (S)-4a and 4c, which were also reliable catalysts, does
not improve the results (entries 3 and 4). We next employed
15
symmetrical catalysts of the type (S,S)-5 to improve the selectivity
of the kinetic resolution. Although symmetrical catalysts (S,S)-5a
and 5b did not show significant improvement of the results (entries
0
5
and 6), switching the 3,3 -aromatic substituents (Ar) of the cat-
alyst (S,S)-5 to radially extended substituents (5cee) resulted in
improved selectivities (s¼11e35, entries 7e10). The best selectivity
was achieved by employment of the catalyst (S,S)-5c (s¼32, entry
7
), and the product (S)-2a was obtained in 81% ee (53% yield) with
Entry
Catalyst
Yield of
ee of 2ac (%)
Yield of
1a (%)
ee of
1a (%)
sd
6.4
1.6
1.6
2.2
4.9
1.3
recovery of the unreacted (R)-1a in 93% ee (43% yield). It should be
noted that the further high enantioselectivity of the allylation
product (S)-2a (90% ee) was obtained in the lower conversion
b
b
c
2a
(%)
1
2
3
4
5
6
7
(S,S)-3a
(S,S)-3c
(S)-4a
15
39
44
68
26
65
53
38
47
29
ꢂ70
ꢂ20
ꢂ17
22
60
8
81
90
70
84
82
57
53
30
69
33
43
60
50
67
ꢂ12
ꢂ8
ꢂ12
40
22
12
93
61
64
38
(
entry 8).
We next examined the effect of protecting groups (X) on the
(S)-4c
nitrogen of 1 in the kinetic resolution under the phase-transfer
conditions (Scheme 2). Although the kinetic resolutions catalyzed
by (S,S)-5c with substrates possessing sulfonyl groups, such as
methanesulfonyl (1b) and p-nitrobenzenesulfonyl (1c) groups, gave
the allylation products 2b and 2c with good selectivities (s¼18e23),
the reaction with amide-type substrates 1d and 1e showed low
reactivities and gave only trace amount of allylation products 2d
and 2e. The substrate 1a possessing benzenesulfonyl group on the
nitrogen was most appropriate substrate in terms of both reactivity
and selectivity for the kinetic resolution under the phase-transfer
conditions.
We also investigated the effect of electrophiles for the kinetic
resolution of (ꢀ)-1a in the presence of catalyst (S,S)-5c (Scheme 3).
The reactions with relatively reactive alkyl iodides, such as benzyl
iodide and methyl iodide, gave alkylation products 2f and 2g in
moderate conversion with good selectivities (s¼13e19). On the
other hand, Michael acceptors, such as methyl vinyl ketone and
phenyl vinyl sulfone, were not appropriate electrophiles for the
(S,S)-5a
(S,S)-5b
(S,S)-5c
(S,S)-5c
(S,S)-5d
(S,S)-5e
32
e
8
9
35
11
17
f
10
a
Reaction conditions: (ꢀ)-1a (0.050 mmol), allyl iodide (0.038 mmol) in the
presence of chiral phase-transfer catalyst (2 mol %) in 50% aqueous KOH (2.0 mL)/
ꢁ
toluene (1.0 mL) at 0 C for 48 h.
b
Isolated yield.
c
Enantiomeric excess (ee) was determined by HPLC analysis using a chiral sta-
tionary phase.
d
The selectivity factor (s) was calculated as follows.8 s¼kfast/kslow¼In
[1ꢂC(1þee2)]/In[1ꢂC(1ꢂee2)]¼In[(1ꢂC)(1ꢂee1)]/In[(1ꢂC)(1þee1)];
C¼ee1/
(
ee1þee2).
e
The reaction was performed for 16 h.
Allyl iodide (0.028 mmol) was used.
f
catalyst (S,S)-5c to provide allylation products 7c and 7d in mod-
erate to high selectivities (s¼4.7e27). These results indicate that
16
kinetic resolution under the phase-transfer conditions. The best
electrophile was allyl iodide in these trials.
With optimal phase-transfer catalyst and reaction conditions in
hand, we studied the generality of the kinetic resolution of 2-
0
the heteroatoms at 2 -position of the binaphthyl core are important
for efficient promotion of the present kinetic resolution.1 Substrate
7
6e possessing tetraline backbone, which was also useful building
0
0
18
amino-1,1 -biaryls (ꢀ)-6 (Scheme 4). Although 2-amino-1,1 -
block, was resolved with high selectivity (s¼37). Other 2-amino-
0
binaphthyls 6a and 6b showed low reactivities for the phase-
1,1 -biaryls 6fej possessing different biaryl skeletons were also
16
transfer-catalyzed N-allylations, the kinetic resolutions with
substrates 6c and 6d possessing a methylthio group and a dime-
thylamino group, respectively, were efficiently promoted by
resolved with moderate to high selectivities (s¼5.7e43). Notably,
introduction of an additional methoxy group onto the phenylamino
moiety improved the selectivities (substrates 6g, 6h vs 6f).
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S. Shirakawa et al. / Tetrahedron xxx (2015) 1e9
3
Scheme 2. Effect of protecting groups.
Scheme 3. Effect of electrophiles.
The protecting groups of the resulting optically enriched start-
ing materials (1a, 6) and allylation products (2a, 7) could be readily
deprotected (Scheme 5). For example, the benzenesulfonyl group of
0
Scheme 4. Kinetic resolution of 2-amino-1,1 -biaryls.
(R)-1a was removed by treatment with low-valent titanium re-
agent, which was generated in situ from titanium(IV) isopropoxide,
19
3. Conclusions
trimethylsilyl chloride, and magnesium powder. Subsequent
0
0
treatment of the resulting 2-amino-2 -methoxy-1,1 -binaphthyl
with boron tribromide gave (R)-NOBIN without any loss of enan-
tioselectivity. Furthermore, (S)-NOBIN was obtained from allylation
product (S)-2a by treatment with diisobutylaluminum hydride
In summary, we have successfully developed an efficient
methodology for the kinetic resolution of 2-amino-1,1 -biaryl
0
compounds via asymmetric N-allylation promoted by binaphthyl-
modified chiral quaternary ammonium salts under the phase-
transfer conditions. Furthermore, this synthetic method could be
extended to the asymmetric desymmetrization of diamino biaryl
compounds. These are valuable examples of catalytic asymmetric
(
DIBAL-H) in the presence of a nickel catalyst for cleavage of allyl
2
0
group on nitrogen and methyl group on oxygen, followed by re-
action with low-valent titanium reagent.
The synthetic utility of this catalytic method for the asymmetric
0
0
synthesis of axially chiral 2-amino-1,1 -biaryls as important chiral
building blocks.
synthesis of 2-amino-1,1 -biaryls were further expanded in the
enantioselective desymmetrization of the diamino compounds 8
(Scheme 6). Attempted reaction of 8a with allyl iodide in aqueous
KOH/toluene under the influence of catalyst (S,S)-5c (2 mol %) at
4. Experimental section
4.1. General
ꢁ
ꢂ5 C for 120 h afforded monoallylation product 9a in moderate
yield with high enantioselectivity (93% ee). Other substrates 8b and
8
c were also employable for the catalytic asymmetric desymmet-
rizations to give axially chiral biaryls 9b and 9c, respectively, in
moderate to good enantioselectivities.
1H NMR spectra were measured on JEOL JNM-FX 400 NMR, JEOL
JNM-AL 400 NMR, and JEOL JNM-ECA 500 NMR instruments (400
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4
S. Shirakawa et al. / Tetrahedron xxx (2015) 1e9
0
corresponding primary 2-amino-1,1 -biaryl compound (0.30 mmol)
and pyridine (4.5 mmol) in dichloromethane (8 mL), and the re-
action mixture was stirred for 24 h at room temperature. The
mixture was concentrated, and the residue was purified by column
chromatography on silica gel (dichloromethane/ethyl acetate/hex-
ane as eluent) to give a starting material 1a or 6 (81e93% yield).
4.4. General procedure for kinetic resolution of 1a and 6
To a solution of starting material 1a or 6 (0.050 mmol) and chiral
phase-transfer catalyst (S,S)-5c (2 mol %, 0.001 mmol) in toluene
1 mL)e50% aqueous KOH (2 mL) was added allyl iodide (0.038mmol)
(
ꢁ
ꢁ
at 0 C. The reaction mixture was vigorously stirred for 48 h at 0 C.
The reaction mixture was quenched with saturated aqueous NH Cl
and extracted with ethyl acetate (3ꢃ5 mL). The combined extracts
were dried over Na SO , and concentrated. The residue was purified
4
Scheme 5. Deprotection of 1a and 2a.
2
4
bycolumn chromatographyor preparative thinlayerchromatography
on silica gel (ethyl acetate/hexane as eluent) to give allylation product
2a or 7 and unreacted starting material 1a or 6.
2
8
4
9
.4.1. Recovered starting material 1a. [
a
]
D
¼ꢂ26.2 (c 0.30, CHCl
3
,
3% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
propanol¼3:1, flow rate¼0.5 mL/min, 231 nm; retention time:
1
1
4.6 min (minor) and 21.0 min (major). H NMR (500 MHz, CDCl
3
)
d
8.11 (d, J¼9.0 Hz, 1H), 8.01 (d, J¼9.5 Hz, 1H), 7.92 (d, J¼9.0 Hz, 1H),
7
7
.82e7.84 (m, 2H), 7.44 (d, J¼8.0 Hz, 2H), 7.40 (d, J¼9.0 Hz, 1H),
.26e7.35 (m, 3H), 7.09e7.15 (m, 3H), 6.95 (t, J¼7.5 Hz, 1H), 6.88 (d,
13
J¼8.5 Hz, 1H), 6.56 (s, 1H), 6.46 (d, J¼8.5 Hz, 1H), 3.67 (s, 3H);
C
3
NMR (125 MHz, CDCl ) d 154.9, 139.2, 133.5, 133.1, 132.9, 132.6,
131.2, 131.0, 129.1, 129.0, 128.6, 128.0, 127.3, 126.9, 126.6, 125.9,
125.0, 124.4, 123.8, 122.6, 119.7, 115.9, 113.2, 56.4; IR (neat) 1592,
1
6
508, 1399, 1316, 1268, 1254, 1167, 1148, 1089, 983, 811, 746, 720,
ꢂ1
þ
87, 582 cm ; HRMS (ESI-TOF) calcd for C27
H
21NO
3
SNa : 462.1134
þ
Scheme 6. Catalytic enantioselective desymmetrization of biaryl compounds.
([MþNa] ), found 462.1115.
and 500 MHz for H NMR). 13C NMR spectra were measured on JEOL
1
28
4
.4.2. Allylation product 2a. [
a
]
D
¼ꢂ24.4 (c 0.60, CHCl
3
, 81% ee);
JNM-FX 400 NMR, JEOL JNM-AL 400 NMR, and JEOL JNM-ECA 500
NMR instruments (100 and 125 MHz for C NMR). Tetramethylsi-
lane (TMS) served as the internal standard (0 ppm) for H NMR, and
3
CDCl served as the internal standard (77.0 ppm) for C NMR. The
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
13
rate¼0.5 mL/min, 225 nm; retention time: 26.6 min (major) and
1
1
3
7
7
2
4
(
1
1
1
6.9 min (minor). H NMR (500 MHz, CDCl
3
)
d
7.99 (d, J¼9.5 Hz,1H),
13
.91e7.95 (m, 2H), 7.88 (d, J¼8.0 Hz, 1H), 7.48e7.62 (br, 1H),
following abbreviations were used to express the multiplicities:
s¼singlet; d¼doublet; t¼triplet; q¼quartet; m¼multiplet;
br¼broad. High performance liquid chromatography (HPLC) was
performed on Shimadzu 10A instruments using Daicel Chiralpak
IA-3 or IB-3 (4.6 mmꢃ250 mm) columns. High-resolution mass
spectra (HRMS) were performed on BRUKER microTOF focuseKR
and JEOL JMS-700N. Optical rotations were measured on a JASCO
DIP-1000 and P-2200 digital polarimeters. All reactions were
monitored by thin-layer chromatography using Merck precoated
TLC plates (silica gel 60GF-254, 0.25 mm), with visualization by
.44e7.48 (t, J¼7.5 Hz, 1H), 7.38 (d, J¼9.5 Hz, 2H), 7.33 (t, J¼7.5 Hz,
H), 7.22e7.26 (m, 3H), 6.96e7.18 (m, 4H), 5.49e5.96 (br, 1H),
13
.78e4.90 (m, 2H), 3.77e3.81 (m, 2H), 3.72 (s, 3H); C NMR
125 MHz, CDCl
33.0, 132.2, 129.9, 128.9, 128.4, 128.3, 128.0, 127.8, 127.7, 126.7,
26.38, 126.35, 123.8, 119.4, 118.9, 112.9, 55.9, 53.6; IR (neat) 1592,
507, 1462, 1446, 1355, 1328, 1270, 1262, 1251, 1158, 1088, 1054,
3
) d 154.4, 140.0, 136.7, 134.5, 134.2, 133.9, 133.2,
ꢂ1
1
C
020, 809, 751, 721, 688, 633, 585 cm ; HRMS (ESI-TOF) calcd for
þ
þ
30
H25NO
3
SNa : 502.1447 ([MþNa] ), found 502.1431.
using UV (254 nm), or dyes such as KMnO
4
. The products were
30
4
7
.4.3. Recovered starting material 1b. [
a
]
D
¼ꢂ16.6 (c 0.20, CHCl
3
,
purified by flash column chromatography on silica gel 60N [Kanto
Chemical Co., Inc. (spherical, neutral)] or Merck preparative thin
layer chromatography on silica gel (PLC 60 F254, 0.5 mm). All
simple chemicals were purchased and used as received.
3% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
propanol¼5:1, flow rate¼0.5 mL/min, 230 nm; retention time:
1
1
d
8.3 min (minor) and 21.3 min (major). H NMR (400 MHz, CDCl
3
)
8.07 (d, J¼9.2 Hz, 1H), 7.98e8.04 (m, 2H), 7.91 (d, J¼8.4 Hz, 2H),
7
.48 (d, J¼9.2 Hz, 1H), 7.35e7.44 (m, 2H), 7.23e7.27 (m, 2H), 7.04 (d,
4
.2. Synthesis of chiral phase-transfer catalysts
J¼8.4 Hz, 1H), 6.98 (d, J¼8.4 Hz, 1H), 6.17 (s, 1H), 3.79 (s, 3H), 2.67 (s,
13
3
3
H); C NMR (100 MHz, CDCl ) d 154.9, 133.5, 133.18, 133.15, 131.41,
Catalysts (S,S)-3,13 (S)-4,14 and (S,S)-515 were prepared according
to the literature.
131.38, 129.5, 129.3, 128.5, 128.1, 127.6, 126.8, 125.9, 125.4, 124.4,
124.3, 123.5, 120.3, 116.2, 113.3, 56.3, 39.7; IR (neat) 1508, 1396,
ꢂ1
1
353, 1315, 1268, 1253, 1158, 1084, 985, 812, 752 cm ; HRMS (ESI-
SNa : 400.0978 ([MþNa]þ), found
þ
4
.3. General procedure for synthesis of starting materials 1a
TOF) calcd for
400.0961.
C
22
H19NO
3
7
and 6
2
9
A
solution of benzenesulfonyl chloride (0.36 mmol) in
4.4.4. Allylation product 2b. [
a
]
D
¼ꢂ19.9 (c 0.50, CHCl
3
, 78% ee);
dichloromethane (2 mL) was added dropwise to a solution of
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼5:1, flow
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S. Shirakawa et al. / Tetrahedron xxx (2015) 1e9
5
1
rate¼0.5 mL/min, 254 nm; retention time: 17.9 min (major) and
33.3 min (minor). H NMR (500 MHz, CDCl
3
)
d
8.02 (d, J¼9.0 Hz,1H),
1
2
2.3 min (minor). H NMR (400 MHz, CDCl
.94 (t, J¼8.8 Hz, 2H), 7.87 (d, J¼8.4 Hz, 1H), 7.56 (d, J¼8.8 Hz, 1H),
.45e7.49 (m, 2H), 7.33 (t, J¼8.0 Hz, 1H), 7.23e7.27 (m, 2H), 7.17 (d,
J¼8.8 Hz, 1H), 7.05e7.12 (br m, 1H), 5.58e5.77 (br, 1H), 4.99e5.06
3
)
d
8.02 (d, J¼8.8 Hz,1H),
7.89e7.90 (m, 2H), 7.82 (d, J¼9.0 Hz, 1H), 7.46 (t, J¼7.5 Hz, 1H), 7.40
(d, J¼9.5 Hz, 1H), 7.33 (t, J¼7.5 Hz, 1H), 7.31 (d, J¼9.0 Hz, 1H),
6.80e7.26 (m, 14H), 4.45 (br d, J¼14.5 Hz, 1H), 4.28e4.36 (br, 1H),
7
7
13
3
3.69 (s, 3H); C NMR (100 MHz, CDCl ) d 154.4, 140.6, 137.1, 135.2,
1
3
(
m, 2H), 3.86e3.97 (br m, 2H), 3.78 (s, 3H), 1.81e2.24 (br, 3H);
NMR (125 MHz, CDCl 154.4, 137.4, 134.1, 133.8, 133.7, 133.6,
32.9, 130.2, 129.9, 128.8, 128.4, 128.0, 127.8, 126.9, 126.5, 126.41,
26.36, 125.8, 124.0, 119.7, 119.4, 113.0, 56.1, 53.9, 41.1; IR (neat)
C
134.4, 134.3, 133.9, 133.0, 131.8, 130.0, 129.7, 129.4, 129.0, 128.2,
128.1, 128.0, 127.8, 127.6, 127.5, 127.4, 126.8, 126.7, 126.4, 126.3,
123.9, 119.6, 113.0, 55.9, 54.9; IR (neat) 1325, 1262, 1250, 1155, 1086,
3
) d
1
1
1
(
ꢂ1
1055, 808, 746, 720, 700, 686 cm ; HRMS (ESI-TOF) calcd for
ꢂ1
þ
þ
506, 1331, 1271, 1262, 1250, 1147, 1088, 1054, 811, 753 cm ; HRMS
C
34
H27NO
3
SNa : 552.1604 ([MþNa] ), found 552.1616.
þ
þ
ESI-TOF) calcd for C25
H23NO
3
SNa : 440.1291 ([MþNa] ), found
3
0
4
40.1290.
4.4.10. Methylation product 2g. [
a
]
D
¼þ20.5 (c 0.50, CHCl
3
, 75% ee);
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
2
9
4
1
.4.5. Recovered starting material 1c. [
a]
D
¼ꢂ23.3 (c 0.40, CHCl
3
,
rate¼0.5 mL/min, 227 nm; retention time: 23.8 min (major) and
1
8% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
35.9 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.86e8.00 (m, 4H),
propanol¼3:1, flow rate¼0.5 mL/min, 254 nm; retention time:
7.53 (d, J¼8.8 Hz, 1H), 7.48 (t, J¼7.4 Hz, 1H), 7.15e7.39 (m, 11H), 3.73
1
13
1
8.2 min (minor) and 23.9 min (major). H NMR (400 MHz, CDCl
8.05 (d, J¼8.8 Hz,1H), 8.00 (d, J¼8.8 Hz, 2H), 7.89 (d, J¼8.4 Hz, 1H),
.74 (d, J¼8.0 Hz, 1H), 7.62 (d, J¼8.8 Hz, 2H), 7.44 (d, J¼9.6 Hz, 1H),
.40 (t, J¼7.6 Hz, 1H), 7.32 (d, J¼9.2 Hz, 2H), 7.12e7.19 (m, 2H), 6.93
3
)
3
(s, 3H), 2.87 (s, 3H); C NMR (100 MHz, CDCl ) d 154.4, 138.7, 138.5,
d
134.5, 134.1, 133.8, 133.0, 132.3, 129.8, 129.3, 128.9, 128.4, 128.0,
127.8, 127.6, 126.9, 126.5, 126.45, 126.39, 126.30, 125.9, 123.7, 119.6,
113.0, 56.0, 38.4; IR (neat) 1593, 1507, 1446, 1353, 1328, 1264, 1248,
7
7
ꢂ1
(
1
s,1H), 6.87 (d, J¼8.8 Hz,1H), 6.81 (t, J¼7.6 Hz,1H), 6.23 (d, J¼8.8 Hz,
1179, 1152, 1088, 1052, 827, 809, 752, 721, 689 cm ; HRMS (ESI-
H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl
)
d
154.1, 149.4, 144.8,
TOF) calcd for C28
4.4.11. Recovered starting material 6a. 1H NMR (400 MHz, CDCl
)
3
H
24NO
S : 454.1471 ([MþH] ), found 454.1457.
þ
þ
3
3
1
1
33.3, 132.9, 132.0, 131.6, 131.2, 129.5, 128.9, 128.1, 128.0, 127.4,
26.8, 126.7, 126.5, 126.0, 125.9, 124.8, 123.9, 123.6, 123.4, 116.8,
1
6
13.4, 56.9; IR (neat) 1528, 1348, 1313, 1268, 1169, 1089, 813, 743,
d
8.14 (d, J¼9.2 Hz, 1H), 7.93e7.98 (m, 3H), 7.87 (d, J¼8.4 Hz, 1H),
ꢂ1
þ
85 cm ; HRMS (FAB) calcd for C27
H
20
N
2
O
5
S: 484.1093 ([M] ),
7.36e7.51 (m, 6H), 7.30 (t, J¼8.4 Hz, 2H), 7.13e7.20 (m, 2H), 6.90 (d,
J¼8.8 Hz, 1H), 6.84 (d, J¼8.8 Hz, 1H), 6.66 (d, J¼7.2 Hz, 1H), 6.24 (s,
found 484.1105.
13
1
3
H); C NMR (100 MHz, CDCl ) d 138.7, 133.8, 133.2, 132.9, 132.4,
2
9
4.4.6. Allylation product 2c. [
a
]
D
¼ꢂ12.9 (c 0.23, CHCl
3
, 90% ee);
132.2, 131.7, 131.0, 129.3, 129.2, 128.9, 128.5, 128.4, 127.9, 127.15,
127.11, 126.8, 126.7, 126.5, 126.1, 125.7, 125.3, 125.0, 120.2; IR (neat)
1447, 1401, 1367, 1323, 1168, 1091, 978, 867, 843, 804, 794, 782, 773,
748, 721, 687, 609, 581, 562 cm ; HRMS (ESI-TOF) calcd for
C
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
rate¼0.5 mL/min, 254 nm; retention time: 20.6 min (major) and
1
ꢂ1
2
5.6 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.98 (d, J¼8.8 Hz,1H),
þ
þ
7
.94 (d, J¼7.6 Hz, 2H), 7.79 (br, 1H), 7.60e7.72 (br m, 2H), 7.49 (t,
26
H19NO
2
SNa : 432.1029 ([MþNa] ), found 432.1017.
J¼7.6 Hz, 1H), 7.37 (d, J¼9.6 Hz, 1H), 7.22e7.31 (m, 4H), 7.15 (t,
J¼8.0 Hz, 1H), 7.06 (br, 2H), 6.94 (d, J¼8.4 Hz, 1H), 5.85 (br, 1H),
4.4.12. Recovered starting material 6b. 1H NMR (400 MHz, CDCl
d
)
3
13
4
.93e5.07 (br m, 2H), 4.05 (br, 2H), 3.74 (s, 3H); C NMR (100 MHz,
8.17 (d, J¼8.8 Hz, 1H), 7.85e7.96 (m, 4H), 7.54 (d, J¼7.2 Hz, 2H),
CDCl
28.8, 128.6, 128.0, 127.6, 126.9, 126.71, 126.68, 126.6, 126.1, 124.0,
23.2, 119.9, 119.3, 113.0, 56.0, 54.8; IR (neat) 1528, 1346, 1261, 1251,
3
)
d
154.2, 149.2, 146.1, 136.0, 134.1, 133.8, 133.1, 130.1, 129.8,
7.46e7.48 (m, 2H), 7.35e7.42 (m, 2H), 7.29 (t, J¼8.0 Hz, 2H), 7.18 (t,
J¼7.6 Hz, 1H), 7.02 (t, J¼7.4 Hz, 1H), 6.83 (d, J¼8.4 Hz, 1H), 6.62 (d,
1
1
13
J¼8.8 Hz, 1H), 6.26 (s, 1H), 1.78 (s, 3H); C NMR (100 MHz, CDCl
3
)
ꢂ1
1161, 1088, 1053, 1019, 808, 747, 736, 686 cm ; HRMS (FAB) calcd
d
139.3, 136.3, 133.0, 132.6, 132.4, 132.3, 130.8, 129.3, 129.2, 129.1,
þ
for C30
24
H N
2
O
5
S: 524.1406 ([M] ), found 524.1406.
129.0, 128.9, 128.2, 128.0, 127.1, 127.0, 125.42, 125.39, 125.1, 124.6,
1
24.1, 118.3, 19.6; IR (neat) 1404, 1313, 1167, 1091, 979, 841, 814, 740,
ꢂ1
4
d
.4.7. Recovered starting material 1d. 1H NMR (400 MHz, CDCl
8.79e8.82 (m, 1H), 8.02e8.10 (m, 2H), 7.92 (d, J¼8.0 Hz, 2H),
3
)
719, 686, 611, 580, 563 cm ; HRMS (FAB) calcd for C27
423.1293 ([M] ), found 423.1308.
H21NO
2
S:
þ
13
7
(
1
1
1
7
.75e7.76 (br, 1H), 7.13e7.60 (m, 12H), 3.77 (s, 3H); C NMR
100 MHz, CDCl 165.1, 155.1, 135.0, 134.5, 133.5, 133.0, 131.5,
31.05, 130.99, 129.3, 128.9, 128.5, 128.2, 128.1, 127.6, 126.6, 126.3,
25.7, 124.9, 124.8, 124.3, 121.5, 120.3, 117.0, 113.6, 56.7; IR (neat)
677, 1596, 1502, 1488, 1428, 1332, 1263, 1250, 1082, 812, 750,
2
9
3
)
d
4.4.13. Recovered starting material 6c. [
38% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
a]
D
¼þ4.1 (c 0.60, CHCl
3
,
propanol¼3:1, flow rate¼0.5 mL/min, 254 nm; retention time:
1
15.0 min (minor) and 18.6 min (major). H NMR (400 MHz, CDCl
3
)
ꢂ1
þ
þ
2
09 cm
;
HRMS (ESI-TOF) calcd for
C
28
H22NO
:
404.1645
d
8.16 (d, J¼9.2 Hz, 1H), 7.97 (t, J¼9.8 Hz, 2H), 7.84 (d, J¼8.0 Hz, 2H),
(
[MþH] ), found 404.1628.
7.49e7.54 (m, 3H), 7.32e7.40 (m, 3H), 7.14e7.23 (m, 3H), 6.95 (t,
J¼7.6 Hz, 1H), 6.82 (d, J¼8.8 Hz, 1H), 6.47 (d, J¼8.4 Hz, 1H), 6.41 (s,
4
d
.4.8. Recovered starting material 1e. 1H NMR (400 MHz, CDCl
8.70 (br, 1H), 8.04 (d, J¼9.2 Hz, 1H), 7.98 (d, J¼9.2 Hz, 1H), 7.88 (d,
3
)
1H), 2.33 (s, 3H); C NMR (100 MHz, CDCl
13
3
)
d
139.4, 138.0, 132.80,
132.75, 132.69, 132.5, 131.1, 130.9, 129.97, 129.95, 129.8, 128.7, 128.1,
127.5, 127.1, 127.0, 125.21, 125.18, 125.16, 124.0, 122.8, 122.3, 118.6,
15.2; IR (neat) 1405, 1306, 1165, 1090, 979, 864, 842, 810, 744, 719,
686, 617, 581 cm ; HRMS (ESI-TOF) calcd for C27
478.0906 ([MþNa] ), found 478.0919.
J¼8.0 Hz, 2H), 7.46 (d, J¼9.2 Hz, 1H), 7.32e7.38 (m, 2H), 7.17e7.24
(
1
d
m, 2H), 7.04e7.08 (m, 3H), 6.02 (d, J¼16.8 Hz, 1H), 5.72e5.78 (br m,
13
ꢂ1
þ
þ
H), 5.46 (d, J¼10.4 Hz, 1H), 3.73 (s, 3H); C NMR (100 MHz, CDCl
163.3, 155.1, 134.2, 133.4, 132.9, 131.5, 131.0, 129.2, 128.7, 128.1,
28.0, 127.4, 126.7, 126.3, 125.7, 124.8, 124.7, 124.2, 121.5, 120.4,
3
)
H21NO
2
S
2
Na :
1
2
9
116.7, 113.5, 56.5; IR (neat) 1682, 1592, 1495, 1427, 1260, 1247, 1084,
4.4.14. Allylation product 7c. [
a]
D
¼ꢂ68.0 (c 0.60, CHCl
3
, 53% ee);
ꢂ1
8
12, 747 cm ; HRMS (FAB) calcd for C24
H
20NO
2
: 354.1494
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
þ
(
[MþH] ), found 354.1498.
rate¼0.5 mL/min, 254 nm; retention time: 16.3 min (major) and
1
41.6 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.94e8.01 (m, 3H),
2
8
4.4.9. Benzylation product 2f. [
a
]
D
¼ꢂ86.8 (c 0.70, CHCl
3
, 83% ee);
7.90 (d, J¼8.4 Hz, 1H), 7.69 (d, J¼8.8 Hz, 1H), 7.42e7.53 (m, 3H),
7.27e7.35 (m, 4H), 7.15 (d, J¼8.4 Hz, 1H), 7.00e7.12 (m, 4H),
5.66e5.76 (m, 1H), 4.89e4.93 (m, 2H), 3.90 (dd, J¼7.8, 15.8 Hz, 1H),
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
rate¼0.5 mL/min, 227 nm; retention time: 24.3 min (major) and
Please cite this article in press as: Shirakawa, S.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.10.074

6
S. Shirakawa et al. / Tetrahedron xxx (2015) 1e9
3
d
.65 (dd, J¼4.4, 15.6 Hz,1H), 2.37 (s, 3H); 13C NMR (125 MHz, CDCl
3
)
d
7.90 (d, J¼9.6 Hz, 1H), 7.83 (d, J¼8.4 Hz, 1H), 7.77 (d, J¼8.0 Hz, 1H),
139.5, 136.4, 135.4, 133.3, 133.25, 133.18, 133.0, 132.3, 131.9, 131.3,
7.41 (dt, J¼1.6, 7.8 Hz, 1H), 7.27e7.34 (m, 4H), 7.22 (dt, J¼1.2, 7.6 Hz,
1H), 7.16 (t, J¼7.6 Hz, 1H), 7.08e7.12 (m, 2H), 6.98 (t, J¼8.0 Hz, 2H),
129.2, 128.88, 128.85, 128.4, 128.2, 128.0, 127.6, 127.0, 126.8, 126.7,
13
126.6, 126.3, 125.6, 123.1, 119.1, 53.2, 15.8; IR (neat) 1350, 1325, 1158,
6.81 (d, J¼8.8 Hz, 1H), 6.68 (s, 1H), 3.81 (s, 3H); C NMR (100 MHz,
ꢂ1
1089, 809, 749, 720, 687, 625, 582, 576, 569 cm ; HRMS (ESI-TOF)
CDCl
128.5,128.4,127.8,127.0,126.7,125.0,124.5,123.8,122.7,119.1,113.0,
6.7; IR (neat) 1447, 1330, 1256, 1159, 1091, 1065, 916, 900, 808, 747,
3
) d 153.3, 139.1, 135.1, 133.3, 132.3, 132.2, 130.7, 129.2, 128.7,
þ
þ
calcd for C30
H25NO S
2 2
Na : 518.1219 ([MþNa] ), found 518.1198.
5
2
5
ꢂ1
þ
4.4.15. Recovered starting material 6d. [
a
]
D
¼ꢂ141.6 (c 0.40, CHCl
3
,
717, 686, 631, 587 cm ; HRMS (ESI-TOF) calcd for C23
412.0978 ([MþNa] ), found 412.0957.
H19NO
3
SNa :
þ
6
7% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
propanol¼3:1, flow rate¼0.5 mL/min, 254 nm; retention time:
1
26
10.3 min (minor) and 11.0 min (major). H NMR (500 MHz, CDCl
3
)
4.4.20. Allylation product 7f. [
a
]
D
¼ꢂ9.2 (c 0.50, CHCl
3
, 62% ee);
d
8.06 (d, J¼8.5 Hz, 1H), 8.01 (s, 1H), 7.93 (d, J¼9.0 Hz, 1H), 7.88 (d,
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
J¼9.5 Hz, 1H), 7.86 (d, J¼8.0 Hz, 1H), 7.70 (d, J¼8.5 Hz, 1H), 7.46 (d,
J¼9.0 Hz, 1H), 7.36 (t, J¼7.5 Hz, 1H), 7.11e7.19 (m, 4H), 6.99 (d,
J¼8.5 Hz, 1H), 6.89 (t, J¼7.8 Hz, 1H), 6.78 (t, J¼7.8 Hz, 1H), 6.70 (t,
rate¼0.5 mL/min, 228 nm; retention time: 16.6 min (minor) and
1
22.1 min (major). H NMR (500 MHz, CDCl
3
)
d
7.90 (d, J¼9.0 Hz, 1H),
7.80e7.84 (m,1H), 7.13e7.48 (m,13H), 5.43e5.70 (br,1H), 4.81e4.92
(m, 2H), 3.80 (s, 3H), 3.58e3.82 (m, 2H); C NMR (125 MHz, CDCl
d 153.6, 140.0, 139.2, 137.0, 133.9, 133.3, 132.9, 132.1, 131.2, 129.6,
128.8,128.4,128.1,128.0,127.7,127.6,126.4,125.9,123.6,122.0,118.7,
112.8, 56.0, 53.5; IR (neat) 1509, 1446, 1331, 1267, 1254, 1159, 1090,
13
13
J¼7.8 Hz, 2H), 6.21 (d, J¼9.0 Hz, 1H), 2.58 (s, 6H); C NMR
3
)
(
1
1
125 MHz, CDCl
30.2, 129.4, 129.0, 128.1, 128.0, 127.5, 127.4, 126.9, 126.6, 126.4,
26.0, 125.5, 125.3, 123.6, 123.4, 121.9, 118.0, 43.4; IR (neat) 1352,
3
)
d
149.0, 139.2, 133.8, 133.6, 132.0, 131.9, 131.6,
ꢂ1
ꢂ1
1306, 1161, 1091, 993, 816, 745, 719, 686, 586 cm ; HRMS (ESI-TOF)
1067, 860, 809, 756, 739, 689, 589 cm ; HRMS (ESI-TOF) calcd for
C
þ
þ
þ
calcd for C28
H
25
N
2
O
2
S: 453.1631 ([MþH] ), found 453.1619.
26
H23NO
3
SNa : 452.1291 ([MþNa] ), found 452.1281.
2
5
24
4
.4.16. Allylation product 7d. [
a
]
D
¼ꢂ8.3 (c 0.40, CHCl
3
, 86% ee);
4.4.21. Recovered starting material 6g. [
a
]
D
¼ꢂ38.8 (c 0.50, CHCl
3
,
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
94% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
rate¼0.5 mL/min, 217 nm; retention time: 13.6 min (major) and
propanol¼3:1, flow rate¼0.5 mL/min, 228 nm; retention time:
1
1
2
6
3
1
1
1
1
C
2.6 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.78e7.94 (m, 4H),
15.6 min (minor) and 20.2 min (major). H NMR (400 MHz, CDCl
3
)
.79e7.66 (m, 13H), 5.55e6.13 (br, 1H), 4.56e5.18 (br, 2H),
d
7.91 (d, J¼9.2 Hz, 1H), 7.78 (d, J¼8.0 Hz, 1H), 7.47 (d, J¼8.4 Hz, 1H),
1
3
.62e4.35 (br, 2H), 2.50 (s, 6H); C NMR (125 MHz, CDCl
40.1 (br), 137.1, 136.2, 135.0, 134.4, 133.9 (br), 133.0, 132.1, 129.2,
28.8 (br), 128.4, 128.2, 128.0, 127.7, 127.6, 127.5, 126.5, 126.3, 126.2,
23.7 (br), 119.0, 118.9, 53.1, 43.3; IR (neat) 1505, 1446, 1330, 1158,
3
) d 149.6,
7.25e7.41 (m, 6H), 7.07e7.14 (m, 3H), 6.72e6.79 (m, 2H), 6.39 (s,
13
3
1H), 3.78 (s, 3H) 3.52 (s, 3H); C NMR (100 MHz, CDCl ) d 157.9,
154.3, 139.1, 136.2, 133.1, 132.5, 130.8, 129.4, 129.1, 128.5, 128.0,
126.9, 124.2, 123.7, 116.1, 115.0, 113.3, 112.9, 107.5, 56.6, 55.8; IR
(neat) 1585, 1466, 1447, 1393, 1328, 1268, 1252, 1164, 1090, 1074,
ꢂ1
089, 812, 751, 720, 688, 579 cm ; HRMS (ESI-TOF) calcd for
þ
ꢂ1
31
29
H N
2
O
2
S: 493.1944 ([MþH] ), found 493.1934.
809, 735, 718, 686, 636, 585 cm ; HRMS (ESI-TOF) calcd for
þ
þ
C
24
H
21NO
4
SNa : 442.1084 ([MþNa] ), found 442.1071.
2
9
4
9
.4.17. Recovered starting material 6e. [
7% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
a
]
D
¼þ5.9 (c 0.50, CHCl
3
,
2
6
4.4.22. Allylation product 7g. [
a
]
D
¼þ3.0 (c 0.50, CHCl
3
, 85% ee);
propanol¼3:1, flow rate¼0.5 mL/min, 218 nm; retention time:
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
1
9
d
.4 min (minor) and 11.3 min (major). H NMR (400 MHz, CDCl
3
)
rate¼0.5 mL/min, 228 nm; retention time: 19.5 min (minor) and
1
7.75 (d, J¼8.4 Hz, 2H), 7.49e7.52 (m, 2H), 7.39e7.43 (m, 2H), 7.09
23.3 min (major). H NMR (400 MHz, CDCl
3
)
d
7.89 (d, J¼9.2 Hz, 1H),
(
(
(
d, J¼8.8 Hz, 1H), 6.99 (d, J¼8.4 Hz, 1H), 6.73 (d, J¼8.4 Hz, 1H), 6.12
7.81e7.84 (m, 1H), 7.30e7.45 (m, 7H), 7.05e7.12 (m, 5H), 5.47e5.58
(br, 1H), 4.78e4.89 (br m, 2H), 3.80 (s, 3H), 3.64 (s, 3H), 3.44e3.71
(m, 2H); C NMR (100 MHz, CDCl ) d 158.8,154.1,140.0,133.8,133.2,
3
13
s, 1H), 3.51 (s, 3H), 2.70e2.75 (m, 4H), 1.50e2.11 (m, 12H); C NMR
100 MHz, CDCl 154.5, 139.9, 137.0, 136.2, 133.1, 132.6, 131.8,
13
3
)
d
1
2
30.49, 130.45, 128.9, 128.8, 127.2, 126.6, 122.4, 115.0, 108.7, 55.4,
132.1,129.4,128.9,128.5,128.3,127.8,127.6,126.3,126.0,125.7,123.6,
118.6,118.2,113.3,111.0, 56.10, 56.07, 53.4; IR (neat) 1465,1329,1254,
9.4, 29.2, 27.2, 26.7, 22.99, 22.98, 22.8, 22.7; IR (neat) 2930, 1474,
ꢂ1
ꢂ1
1447, 1384, 1331, 1313, 1260, 1164, 1088, 718, 688, 584 cm ; HRMS
1159, 1088, 1065, 809, 747, 730 cm ; HRMS (ESI-TOF) calcd for
þ
þ
þ
þ
(
ESI-TOF) calcd for C27
H29NO
3
SNa : 470.1760 ([MþNa] ), found
C
27
H
25NO
4
SNa : 482.1397 ([MþNa] ), found 482.1383.
470.1761.
2
8
4
.4.23. Recovered starting material 6h. [
a
]
D
¼þ29.6 (c 0.60, CHCl
3
,
3
0
4.4.18. Allylation product 7e. [
a
]
D
¼ꢂ7.3 (c 0.60, CHCl
3
, 80% ee);
60% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
propanol¼3:1, flow rate¼0.5 mL/min, 230 nm; retention time:
1
rate¼0.5 mL/min, 207 nm; retention time: 11.0 min (major) and
15.0 min (minor) and 18.7 min (major). H NMR (400 MHz, CDCl
3
)
1
2
3.9 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.44e7.49 (m, 3H),
d
7.88 (d, J¼9.2 Hz,1H), 7.76 (d, J¼8.4 Hz,1H), 7.24e7.41 (m, 5H), 7.13
7
.29e7.33 (m, 2H), 7.05e7.14 (m, 3H), 6.76 (d, J¼8.4 Hz, 1H),
(t, J¼7.6 Hz, 1H), 7.10 (dt, J¼1.2, 7.8 Hz, 1H), 6.98e7.01 (m, 3H), 6.85
5
3
.63e5.73 (m, 1H), 4.84e4.92 (m, 2H), 3.70e3.72 (m, 2H), 3.64 (s,
(d, J¼8.4 Hz, 1H), 6.78 (dd, J¼2.4, 8.8 Hz, 1H), 6.67 (s, 1H), 3.88 (s,
13
13
H), 2.57e2.84 (m, 5H), 2.01e2.22 (m, 3H), 1.55e1.79 (m, 8H);
154.1, 140.8, 137.60, 137.58, 137.4, 135.0,
33.51, 133.48, 132.2, 130.2, 129.0, 128.6, 128.5, 128.2, 127.8, 126.0,
18.4, 107.9, 54.9, 53.8, 29.9, 29.4, 27.4, 27.0, 23.04, 22.96, 22.7; IR
C
3H) 3.80 (s, 3H); C NMR (100 MHz, CDCl
3
)
d
159.7, 153.6, 139.0,
NMR (100 MHz, CDCl
3
)
d
136.0, 133.7, 132.8, 132.3, 130.4, 129.2, 128.4, 127.8, 126.9, 126.7,
124.6, 123.7, 120.2, 118.9, 113.0, 111.3, 107.6, 56.7, 55.4; IR (neat)
1614, 1506, 1331, 1291, 1259, 1171, 1158, 1091, 1067, 809, 730,
1
1
ꢂ1
þ
þ
(
neat) 2930, 1482, 1474, 1446, 1351, 1324, 1262, 1157, 1088, 1039,
686 cm ; HRMS (ESI-TOF) calcd for C24
H
21NO
4
SNa : 442.1084
ꢂ1
þ
8
03, 757, 720, 689 cm ; HRMS (ESI-TOF) calcd for C30
H33NO
3
SNa :
([MþNa] ), found 442.1070.
þ
510.2073 ([MþNa] ), found 510.2058.
2
9
4
.4.24. Allylation product 7h. [
a
]
D
¼ꢂ2.2 (c 0.45, CHCl
3
, 82% ee);
2
6
4
.4.19. Recovered starting material 6f. [
4% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
propanol¼3:1, flow rate¼0.5 mL/min, 254 nm; retention time:
a]
D
¼ꢂ1.3 (c 0.40, CHCl
3
,
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
7
rate¼0.5 mL/min, 230 nm; retention time: 16.6 min (minor) and
1
18.5 min (major). H NMR (400 MHz, CDCl
3
)
d
7.89 (d, J¼9.2 Hz, 1H),
1
14.3 min (minor) and 18.5 min (major). H NMR (400 MHz, CDCl
3
)
7.80e7.83 (m, 1H), 6.94e7.45 (m, 12H), 5.52e5.69 (br, 1H),
Please cite this article in press as: Shirakawa, S.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.10.074

S. Shirakawa et al. / Tetrahedron xxx (2015) 1e9
7
4
.83e4.93 (m, 2H), 3.86 (s, 3H), 3.81 (s, 3H), 3.59e3.84 (m, 2H); 13
NMR (100 MHz, CDCl 159.0, 154.0, 140.2, 140.1, 134.3, 133.3,
32.2, 129.4, 128.9, 128.8, 128.4, 127.8, 127.6, 126.4, 125.9, 123.6,
21.8, 118.6, 116.6, 114.1, 112.8, 56.0, 55.4, 53.6; IR (neat) 1607, 1505,
C
(0.075 mmol) under argon atmosphere, and the resulting mixture
was stirred for 20 h at 50 C. The reaction mixture was quenched
with 1M aqueous NaOH (0.50 mL), and the mixture was stirred for
30 min. The resulting solution was filtered over Celite, and the fil-
trate was diluted with water. The solution was extracted with ethyl
ꢁ
3
)
d
1
1
1446, 1329, 1286, 1260, 1239, 1163, 1090, 1068, 1038, 910, 809, 751,
ꢂ1
þ
723, 689 cm ; HRMS (ESI-TOF) calcd for C27
H25NO
4
SNa : 482.1397
acetate (3ꢃ5 mL). The combined extracts were dried over Na
2
SO
4
,
þ
0
0
(
[MþNa] ), found 482.1382.
and concentrated to give crude 2-amino-2 -methoxy-1,1 -
0
0
binaphthyl. To a solution of crude 2-amino-2 -methoxy-1,1 -
binaphthyl in dichloromethane (3 mL) was added dropwise boron
3
1
4.4.25. Recovered starting material 6i. [
a
]
D
¼ꢂ4.1 (c 0.50, CHCl
3
,
ꢁ
37% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
tribromide (0.70 mmol) at 0 C under argon atmosphere, and the
ꢁ
propanol¼20:1, flow rate¼0.5 mL/min, 219 nm; retention time:
resulting mixture was stirred for 3 h at 0 C. The mixture was
1
21.1 min (major) and 21.9 min (minor). H NMR (400 MHz, CDCl
3
)
quenched with water, and extracted with ethyl acetate (3ꢃ5 mL).
d
7.70 (d, J¼8.4 Hz, 2H), 7.58 (d, J¼8.4 Hz, 1H), 7.51 (t, J¼7.2 Hz, 1H),
.37e7.41 (m, 2H), 7.29 (t, J¼7.6 Hz, 1H), 7.19 (t, J¼7.6 Hz, 1H), 6.99
d, J¼7.6 Hz, 1H), 6.87 (d, J¼7.6 Hz, 1H), 6.80 (d, J¼8.4 Hz, 1H), 6.20
2 4
The combined extracts were dried over Na SO , and concentrated.
7
The residue was purified by preparative thin layer chromatography
on silica gel (hexane/ethyl acetate¼3/1 as eluent) to give (R)-NOBIN
(0.22 mmol, 86% yield). The enantiomeric excess of (R)-NOBIN was
determined by HPLC analysis.
(
(
13
s, 1H), 3.56 (s, 3H), 1.83 (s, 3H), 1.59 (s, 3H); C NMR (100 MHz,
156.7, 139.8, 138.8, 137.7, 134.4, 132.7, 129.7, 128.8, 128.0,
27.4, 127.2, 125.7, 123.12, 123.06, 116.0, 108.5, 55.5, 19.8, 18.9; IR
3
CDCl ) d
1
(
8
C
neat) 1579,1465,1447,1383,1327,1290,1256,1161,1090,1081, 962,
4.5.2. Deprotection of 2a. To a solution of (S)-2a (0.020 mmol) and
NiCl (dppp) (5 mol %, 0.001 mmol) in toluene (0.20 mL) was added
2
ꢂ1
56, 778, 750, 718, 687, 587 cm ; HRMS (ESI-TOF) calcd for
þ
þ
21
H21NO
3
SNa : 390.1134 ([MþNa] ), found 390.1123.
a 1M solution of diisobutylaluminum hydride in toluene (0.10 mL,
ꢁ
0
.10 mmol) at 0 C, and the reaction mixture was stirred for 3 h at
3
0
4
.4.26. Allylation product 7i. [
a
]
D
¼þ22.9 (c 0.40, CHCl
3
, 60% ee);
room temperature. The mixture was quenched with 1M aqueous
NaOH (0.20 mL), and the mixture was diluted with water. The so-
lution was extracted with ethyl acetate (3ꢃ5 mL). The combined
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼20:1,
flow rate¼0.5 mL/min, 250 nm; retention time: 26.2 min (minor)
1
and 27.0 min (major). H NMR (500 MHz, CDCl
3
)
d
7.46e7.53 (m,
2 4
extracts were dried over Na SO , and concentrated to give a crude
3
6
3
H), 7.23e7.36 (m, 5H), 7.15 (d, J¼7.5 Hz, 1H), 6.96 (d, J¼7.5 Hz, 1H),
N-benzenesulfonyl-protected NOBIN. Deprotection of benzene-
.80 (d, J¼8.5 Hz, 1H), 5.59e5.67 (m, 1H), 4.84e4.92 (m, 2H),
sulfonyl group was carried out as described in the deprotection of
13
19
.74e3.76 (m, 2H), 3.65 (s, 3H), 2.06 (s, 3H), 1.98 (s, 3H); C NMR
156.3, 140.5, 138.8, 138.1, 137.9, 133.3, 132.3,
29.7, 128.6, 128.4, 128.0, 127.3, 126.6, 122.9, 118.4, 107.7, 55.0, 53.8,
(R)-1a. The resulting crude material was purified by thin layer
(
125 MHz, CDCl
3
)
d
chromatography on silica gel (hexane/ethyl acetate¼3/1 as eluent)
to give (S)-NOBIN (0.016 mmol, 80% yield). The enantiomeric excess
of (S)-NOBIN was determined by HPLC analysis.
1
2
0.0, 19.7; IR (neat) 1466, 1446, 1350, 1324, 1309, 1293, 1254, 1157,
ꢂ1
1082, 822, 774, 755, 725, 689, 596 cm ; HRMS (ESI-TOF) calcd for
þ
þ
21
30
C
24
H
25NO
3
SNa : 430.1447 ([MþNa] ), found 430.1438.
4.5.3. (R)- and (S)-NOBIN. (R)-NOBIN: [
a
]
D
¼þ96.0 (c 0.45, THF,
21b
19
9
3% ee) {lit.
[a]
D
¼þ122 [c 1.0, THF, 99% ee (R)]}. (S)-NOBIN:
2
9
30
21a
4.4.27. Recovered starting material 6j. [
a]
D
¼þ26.8 (c 0.50, CHCl
3
,
[a
]
D
¼ꢂ77.6 (c 0.45, THF, 81% ee) {lit.
[
a]
D
¼ꢂ117 [c 1.0, THF,
47% ee); HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
>98% ee (S)]}. HPLC analysis: Daicel Chiralpak IA-3, hexane/2-
propanol¼3:1, flow rate¼0.5 mL/min, 258 nm; retention time:
propanol¼3:1, flow rate¼0.5 mL/min, 228 nm; retention time:
1
1
1
7.0 min (minor) and 23.3 min (major). H NMR (400 MHz, CDCl
3
)
15.9 min (R) and 24.5 min (S). H NMR (400 MHz, CDCl
3
)
d
7.92 (d,
d
7.89 (d, J¼8.8 Hz, 1H), 7.80 (d, J¼8.0 Hz, 1H), 7.54 (d, J¼8.0 Hz, 2H),
J¼9.2 Hz, 1H), 7.84e7.87 (m, 2H), 7.79e7.81 (m, 1H), 7.04e7.39 (m,
13
7
.34e7.46 (m, 4H), 7.23e7.26 (m, 2H), 7.12 (t, J¼8.0 Hz, 1H), 6.95 (d,
8H), 5.15 (br s, 1H), 3.75 (br s, 2H); C NMR (125 MHz, CDCl
3
)
J¼8.4 Hz, 1H), 6.75e6.80 (m, 2H), 6.27 (s, 1H) 3.88 (s, 3H), 2.41 (s,
d
151.8, 143.7, 134.1, 133.2, 130.6, 130.3, 129.5, 128.4, 128.3, 128.2,
13
3
1
1
1
H); C NMR (100 MHz, CDCl
3
)
d
160.4, 139.2, 137.3, 135.8, 133.0,
127.3, 126.9, 124.5, 123.7, 123.6, 122.7, 118.2, 117.7, 114.3, 108.5; IR
ꢂ1
32.8,132.3,131.1,129.6,129.5,128.7,128.0,127.3, 127.2,125.1, 124.2,
(neat) 1617, 1595, 1381, 1216, 1175, 1146, 823, 750 cm ; HRMS (ESI-
þ
22.1, 120.2, 110.8, 105.1, 55.4, 15.4; IR (neat) 1612, 1509, 1500, 1396,
TOF) calcd for C20
H
16NO: 286.1226 ([MþH] ), found 286.1221.
ꢂ1
þ
333, 1293, 1158, 1123, 1091, 884, 806, 741, 719, 687, 595 cm
;
þ
4.6. Synthesis of starting materials 87,22
HRMS (ESI-TOF) calcd for C24
found 458.0845.
H21NO S
3 2
Na : 458.0855 ([MþNa] ),
To a mixture of 1-bromo-2-methoxynaphthalene (2.3 mmol)
and magnesium turnings (9.0 mmol) in diethyl ether (10 mL) was
stirred at room temperature under argon atmosphere until white
slurry was formed. To the resulting mixture was added benzene
(10 mL) to dissolve the material, and the mixture was stirred for 2 h
at room temperature under argon atmosphere. The solution of
resulting Grignard reagent was added dropwise to a solution of 2-
methoxy-1,3-dinitrobenzene (1.5 mmol) in benzene (15 mL), and
2
9
4
.4.28. Allylation product 7j. [
a
]
D
¼ꢂ26.7 (c 0.50, CHCl
3
, 72% ee);
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼3:1, flow
rate¼0.5 mL/min, 254 nm; retention time: 18.2 min (major) and
1
2
0.0 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.85 (t, J¼8.0 Hz, 2H),
7
3
d
.04e7.55 (m, 12H), 5.58e5.69 (m, 1H), 4.90e4.95 (m, 2H), 3.88 (s,
13
H), 3.61e3.84 (m, 2H), 2.43 (s, 3H); C NMR (100 MHz, CDCl
159.5, 139.7, 139.5, 135.5, 133.9, 133.4, 133.1, 132.3, 131.1, 129.9,
28.5, 128.4, 128.0, 127.5, 126.9, 126.7, 125.3, 122.7, 118.9, 116.9,
14.3, 55.4, 53.5, 15.9; IR (neat) 1605, 1509, 1498, 1446, 1325, 1288,
3
)
ꢁ
1
1
1
the mixture was stirred for 8 h at 50 C. The reaction mixture was
quenched with water and extracted with ethyl acetate (3ꢃ15 mL).
ꢂ1
þ
159, 1089, 1036, 829, 808, 750, 722, 688 cm ; HRMS (ESI-TOF)
2 4
The combined extracts were dried over Na SO , and concentrated.
þ
calcd for C27
H25NO
3
S
2
Na : 498.1168 ([MþNa] ), found 498.1159.
The residue was purified by column chromatography on silica gel
ethyl acetate/hexane as eluent) to give a precursor of the starting
material, which was the corresponding dinitro compound
1.1 mmol, 73% yield). A mixture of the corresponding dinitro
(
4
.5. Deprotection of 1a and 2a19,20
(
4
.5.1. Deprotection of 1a. To a mixture of (R)-1a (0.025 mmol) and
compound (1.0 mmol) and Pd/C (80 mg; 10 wt %) in ethanol (10 mL)
was stirred for 12 h at room temperature under hydrogen atmo-
sphere (H balloon). The reaction mixture was filtered over Celite
2
magnesium powder (0.25 mmol) in THF (0.30 mL) was added
titanium(IV) isopropoxide (0.05 mmol) and trimethylsilyl chloride
Please cite this article in press as: Shirakawa, S.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.10.074

8
S. Shirakawa et al. / Tetrahedron xxx (2015) 1e9
and concentrated to give a diamino compound. To a solution of the
resulting diamino compound and pyridine (30 mmol) in dichloro-
methane (20 mL) was added dropwise a solution of benzene-
sulfonyl chloride (3.0 mmol) in dichloromethane (10 mL), and the
reaction mixture was stirred for 24 h at room temperature. The
mixture was concentrated, and the residue was purified by column
chromatography on silica gel (dichloromethane/ethyl acetate/hex-
ane as eluent) to give starting material 8a (0.98 mmol, 98% yield).
Compounds 8b and 8c were synthesized by the same procedure.
TOF) calcd for
607.1335.
C
32
H
28
N
2
O
5
S
2
Na: 607.1332 ([MþNa]þ), found
2
9
4.7.2. Allylation product 9b. [
a
]
D
¼þ21.7 (c 0.20, CHCl
3
, 75% ee);
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼5:1, flow
rate¼0.5 mL/min, 254 nm; retention time: 22.9 min (major) and
1
33.6 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.75e7.80 (m, 3H),
7.26e7.55 (m, 9H), 7.20 (d, J¼8.8 Hz, 1H), 7.03 (d, J¼7.6 Hz, 1H), 6.76
(d, J¼8.8 Hz, 1H), 6.30 (s, 1H), 5.40e5.59 (br m, 1H), 4.76e4.89 (m,
2H), 3.59e3.69 (br m, 2H), 3.52 (s, 3H), 2.73e2.86 (m, 2H),
.6.1. Starting material 8a. 1H NMR (400 MHz, CDCl
)
d
8.01 (d,
2.41e2.51 (br m, 1H), 1.52e1.71 (m, 3H), 1.44e1.50 (m, 2H);
13
C
4
3
J¼8.8 Hz, 1H), 7.83 (d, J¼8.4 Hz, 1H), 7.53 (d, J¼8.4 Hz, 2H),
NMR (100 MHz, CDCl 151.3,140.1,139.4,138.9,136.3,133.1,132.8,
132.5, 131.2, 129.0, 128.8, 128.7, 128.6, 128.4, 127.8, 127.2, 126.5,
3
) d
7.40e7.44 (m, 6H), 7.30e7.36 (m, 3H), 7.20e7.24 (m, 4H), 7.01 (t,
1
3
J¼8.0 Hz, 1H), 6.38 (d, J¼8.8 Hz, 1H), 6.01 (s, 2H), 3.65 (s, 3H);
C
121.2, 120.0, 118.8, 116.8, 108.5, 55.0, 53.8, 29.3, 26.5, 22.7, 22.6; IR
ꢂ1
NMR (125 MHz, CDCl
3
)
d
154.9, 139.1, 135.9, 132.8, 132.6, 132.2,
(neat) 1458, 1447, 1353, 1325, 1229, 1217, 1164, 1091, 581 cm
;
þ
129.5, 129.1, 128.7, 128.5, 127.0, 124.4, 122.6, 117.3, 115.7, 112.8, 111.4,
HRMS (FAB) calcd for C32
589.1832.
H N
33 2
O
5
S
2
: 589.1831 ([MþH] ), found
5
6
6.3; IR (neat) 1464, 1397, 1321, 1269, 1252, 1165, 1090, 748,
ꢂ1
88 cm ; HRMS (ESI-TOF) calcd for C29
H N
24 2
O
5
2
S Na: 567.1019
þ
29
(
[MþNa] ), found 567.1034.
4.7.3. Allylation product 9c. [
a
]
D
¼ꢂ2.4 (c 0.12, CHCl
3
, 46% ee);
HPLC analysis: Daicel Chiralpak IA-3, hexane/2-propanol¼5:1, flow
4
.6.2. Starting material 8b. 1H NMR (400 MHz, CDCl
3
)
d
7.68e7.70
rate¼0.5 mL/min, 254 nm; retention time: 44.7 min (major) and
1
(
7
1
d
m, 4H), 7.50e7.55 (m, 2H), 7.39e7.44 (m, 6H), 7.17e7.22 (m, 2H),
.75 (d, J¼8.8 Hz,1H), 6.03 (s, 2H), 3.41 (s, 3H), 2.73 (t, J¼6.2 Hz, 2H),
55.8 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.75e7.77 (m, 3H),
7.27e7.58 (m, 10H), 6.95e7.00 (m, 2H), 6.81 (d, J¼8.0 Hz, 1H), 6.28
13
.51e1.64 (m, 4H), 1.37e1.41 (m, 2H); C NMR (100 MHz, CDCl
154.9, 139.3, 138.3, 135.3, 133.0, 132.6, 131.5, 129.1, 128.9, 127.1,
17.6, 116.7, 113.3, 109.2, 55.5, 29.0, 26.2, 22.7, 22.4; IR (neat) 1463,
3
)
(s, 1H), 5.50 (br, 1H), 4.77e4.91 (m, 2H), 3.60e3.75 (m, 2H), 3.55 (s,
13
3
3H), 1.80 (s, 3H); C NMR (100 MHz, CDCl ) d 156.9, 140.0, 139.5,
1
1
139.3, 136.3, 133.1, 132.8, 132.6, 130.3, 129.0, 128.8, 128.7, 128.5,
128.0, 127.2, 126.1, 123.5, 120.8, 118.6, 117.7, 111.7, 108.3, 55.1, 53.9,
19.4; IR (neat) 1459, 1447, 1327, 1257, 1160, 1089, 752, 688,
ꢂ1
395, 1333, 1317, 1261, 1164, 1089, 1018, 748, 736, 686, 582 cm
;
þ
HRMS (FAB) calcd for C29
5
29
H N
2
O
5
S
2
: 549.1518 ([MþH] ), found
ꢂ1
þ
49.1519.
.6.3. Starting material 8c. 1H NMR (400 MHz, CDCl
) d 7.62e7.65
3
584 cm ; HRMS (FAB) calcd for C29
H
29
N
2
O
5
S
2
: 549.1518 ([MþH] ),
found 549.1525.
4
(
m, 4H), 7.53 (dt, J¼1.6, 7.4 Hz, 2H), 7.34e7.44 (m, 7H), 7.24 (t,
J¼8.0 Hz, 1H), 6.86 (d, J¼7.6 Hz, 1H), 6.81 (d, J¼8.8 Hz, 1H), 6.03 (s,
4.8. Determination of absolute configurations of 1, 2, 6, 7,
1
3
2
1
1
1
H), 3.47 (s, 3H), 1.32 (s, 3H); C NMR (100 MHz, CDCl
40.0, 139.5, 135.2, 133.0, 131.4, 129.2, 129.0, 127.1, 123.8, 117.84,
17.79, 114.6, 109.0, 55.6,18.6; IR (neat) 1467, 1397, 1382, 1326, 1260,
3
) d 157.0,
and 9
The absolute configurations of compounds 1a and 2a were
confirmed after the transformation to NOBIN as shown in Scheme 5
and Experimental section 4, by comparison of the optical rotation
ꢂ1
165, 1089, 1021, 718, 686, 584 cm ; HRMS (FAB) calcd for
þ
C
H
26 25
N
2
O
5
S
2
: 509.1205 ([MþH] ), found 509.1208.
21
with the literature value. The absolute configurations of 6d and
d were confirmed by comparison of the optical rotation and the
retention time of HPLC with authentic samples, which were pre-
7
4
.7. General procedure for catalytic enantioselective de-
symmetrization of 8
23
pared from commercially available (R)-BINAM.
configuration of compound 6e was confirmed after the trans-
formation to H -NOBIN, by comparison of the retention time of
The absolute
To a solution of starting material 8 (0.026 mmol) and chiral
phase-transfer catalyst (S,S)-5c (2 mol %, 0.0004 mmol) in toluene
8
24
HPLC with the literature value. The absolute configuration of
compound 6f was assigned after the cleavage of benzenesulfonyl
group, by comparison of the retention time of HPLC with the lit-
(
0.5 mL)e50% aqueous KOH (0.5 mL) was added allyl iodide
ꢁ
(
0.020 mmol) at ꢂ5 C. The reaction mixture was vigorously stirred
ꢁ
for 48e168 h at ꢂ5 C. The reaction mixture was quenched with
6b
erature value. The absolute configurations of other compounds 1,
saturated aqueous NH
4
Cl and extracted with ethyl acetate
SO , and
2, 6, and 7 were assigned by analogy. The absolute configurations of
(
3ꢃ5 mL). The combined extracts were dried over Na
2
4
compounds 9 were also tentatively assigned by analogy.
concentrated. The residue was purified by preparative thin layer
chromatography on silica gel (ethyl acetate/hexane as eluent) to
give allylation product 9. Yield of 9 was determined on the basis of
amount of allyl iodide.
Acknowledgements
3
3
This work was partially supported by a Grant-in-Aid for Scien-
tific Research on Innovative Areas ‘Advanced Molecular Trans-
formations by Organocatalysts’ from MEXT (Japan) and Nagase
Science and Technology Foundation. X.W. thanks the financial
support from China Scholarship Council.
4
.7.1. Allylation product 9a. [
a
]
D
¼ꢂ34.8 (c 0.40, THF, 93% ee);
HPLC analysis: Daicel Chiralpak IB-3, hexane/2-propanol¼2:1, flow
rate¼0.4 mL/min, 231 nm; retention time: 22.2 min (major) and
1
2
7
(
3
1
1
1
1
7.7 min (minor). H NMR (400 MHz, CDCl
3
)
d
7.98 (d, J¼8.8 Hz, 1H),
.84 (t, J¼7.0 Hz, 2H), 7.24e7.50 (m, 9H), 6.81e7.19 (br m, 7H), 6.30
br s, 1H), 5.28e5.53 (br, 1H), 4.70e4.86 (br m, 2H), 3.77 (s, 3H),
.38e3.57 (br m, 2H); 13C NMR (125 MHz, CDCl
154.3, 140.1,
39.4, 139.0, 136.9, 133.1, 133.0, 132.7, 132.4, 131.4, 129.0, 128.9,
28.8,128.4,127.9,127.6,127.2,126.8,124.7, 124.2,118.8,118.5,114.8,
12.5, 55.9, 53.6; IR (neat) 2957, 2923, 2853, 2361, 1460, 1447, 1326,
3
) d
Supplementary data
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2015.10.074.
ꢂ1
258, 1161, 1089, 1064, 1023, 807, 749, 737, 687 cm ; HRMS (ESI-
Please cite this article in press as: Shirakawa, S.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.10.074

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9
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Please cite this article in press as: Shirakawa, S.; et al., Tetrahedron (2015), http://dx.doi.org/10.1016/j.tet.2015.10.074