Asymmetric cyclopropanation and aziridination reactions of olefins catalyzed by Cu(I)-binaphthyldiimine complexes

Article abstract of DOI:10.1246/bcsj.76.189

The chiral Cu(I)-N,N′-bis(2,6-dichlorobenzylidene)-1,1′-binaphthyl-2, 2′-diamine complex was found to be an efficient catalyst for asymmetric cyclopropanation and aziridination reactions of olefins with l-menthyl diazoacetate and [N-(p-tolylsulfonyl)imino

Full text of DOI:10.1246/bcsj.76.189

c. Jpn.
© 2003 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 76, 189–199 (2003)
189
e Chemical
ciety of Ja-
n
e Chemical
ciety of Ja-
n
Asymmetric Cyclopropanation and Aziridination Reactions of Olefins
Catalyzed by Cu(Ⅰ)-Binaphthyldiimine Complexes
Cu(Ⅰ)-BINIM-Catalyzed Asymmetric Reactions
H. Suga et al.
Hiroyuki Suga,* Akikazu Kakehi, Suketaka Ito, Toshikazu Ibata,† Tomomi Fudo,† Yuzuru Watanabe,
03
9
and Yoshinori Kinoshita
9
Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University,
Wakasato, Nagano 380-8553
SJA8
09-2673
239
†Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043
(Received August 20, 2002)
02
The chiral Cu(Ⅰ)-N,Nꢀ-bis(2,6-dichlorobenzylidene)-1,1ꢀ-binaphthyl-2,2ꢀ-diamine complex was found to be an effi-
cient catalyst for asymmetric cyclopropanation and aziridination reactions of olefins with l-menthyl diazoacetate and [N-
(p-tolylsulfonyl)imino]phenyliodinane, respectively. Among mono- and disubstituted olefins, 1,1-diarylethylenes
showed extremely high enantioselectivities (up to 98% ee) in the cyclopropanation reactions in the presence of a chiral
Cu(Ⅰ)-catalyst (2 mol%). In the case of aziridination reactions catalyzed by the same Cu(Ⅰ)-catalyst (10 mol%), the reac-
tion of trans-substituted 3-aryl-2-propenoates and 1-substituted trans-3-aryl-2-propen-1-ones showed satisfactory results
in term of the enantioselectivities (up to 98% ee).
02
0.3
It is well-known that chiral binaphthyl derivatives, such as
1,1ꢀ-binaphthyl-2,2ꢀ-diol1 and 1,1ꢀ-dinaphthyl-2,2ꢀ-bisphos-
phine2 derivatives, are highly efficient ligands in asymmetric
synthesis.3 Concerning the mechanistic aspects, the C2-sym-
metry of the axial chirality in the binaphthyl moiety plays an
important role for asymmetric induction. On the other hand,
chiral diimino compounds, such as bis(oxazoline)s4 and
salens,5 are also known to be highly effective ligands in asym-
metric synthesis.3 Since chiral binaphthyldiimines have both
axial chirality and a diimine structure, these derivatives are ex-
pected to serve as effective ligands in enatioselective reactions.
Furthermore, those ligands could coordinate to metal of differ-
Scheme 1.
ent sizes by changing in the dihedral angle between the two
naphthyl rings with flexibility; the resulting complexes may
by mixing CuOTf•0.5C6H6 with several (R)-binaphthyl-
diimines ((R)-BINIMs), which were prepared by the reaction
of (R)-1,1ꢀ-dinaphthyl-2,2ꢀ-diamine with 2,6-dichlorobenzal-
dehyde, 2,6-dinitrobenzaldehyde, 9-anthracenecarboxalde-
hyde, or 3,5-bis(benzyloxy)benzaldehyde, in dichloromethane
at room temperature for 1 h under an argon atmosphere.
Among the BINIMs used, N,Nꢀ-bis(2,6-dichlorobenzylidene)-
1,1ꢀ-binaphthyl- 2,2ꢀ-diamine (BINIM-DC) exhibited moder-
ate enantioselectivity (trans-adduct 3a: 34% ee, cis-adduct 4a:
47% ee, trans:cis = 79:21) in 75% total yield (Table 1, Entry
1).13 Next, the steric effect of the alkoxy group on diazoacetate
(Entries 2 and 3) and the solvent effect (Entries 4–8) were
examined. Higher trans-selectivity was observed with larger
alkoxy substituents, and an l-menthyloxy group on the diazo-
acetate showed the best results in terms of the enantio-
selectivity26 of trans-product 3c. From an investigation of the
solvents, CH2Cl2 showed the highest enantioselectivity for
both trans- and cis-cyclopropanes. The substituent effect of
the benzene ring in the ligands for enantioselectivity was also
create unique chiral environments for highly enantioselective
reactions by placing appropriate substituents on the imino-
carbons. Among this type of chiral binaphthyldiimine ligand,
however, salen-type ligands containing 2-hydroxybenzylidene
moieties were mainly paid attention, and have been applied to
asymmetric synthesis.6 Few examples were reported using
simple chiral binaphthyldiimines having only a diimino-func-
tionality for the coordination site.8,11d In this paper, we provide
a full account of our investigations dealing with the combina-
tion of bidentate chiral binaphthyldiimines and Cu(Ⅰ) salts as a
catalytic system operated efficiently in the enantioselective
cyclopropanation7,8 and aziridination9–12 reactions.
Results and Discussion
Cyclopropanation Reactions of Styrene. Initially, a cy-
clopropanation reaction of styrene (2) with ethyl diazoacetate
(1a) was investigated in the presence of several Cu(Ⅰ)-binaph-
thyldiimine-complexes (1 mol%) in dichloromethane at room
temperature (Scheme 1). The complexes were prepared in situ

190 Bull. Chem. Soc. Jpn., 76, No. 1 (2003)
Cu(ꢀ)-BINIM-Catalyzed Asymmetric Reactions
Table 1. Cu(Ⅰ)-BINIM-Catalyzed Cyclopropanation Reactions of Styrene (2) with Diazoacetate 1a)
Entry
R
Ligand
Solvent
Yield/% trans:cisb) % eeb) trans
cis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Et
t-Bu
BINIM-DC
BINIM-DC
CH2Cl2
CH2Cl2
CH2Cl2
CHCl3
CH3CHCl2
75
77
81
84
81
83
88
83
85
95
87
84
89
86
79:21
81:19
83:17
77:23
73:27
76:24
71:29
81:19
75:25
81:19
73:27
69:31
71:29
77:23
34c)
50c)
57
42
27
34
10
0
39
50
36
15
37
24
47c)
28c)
43
35
7
13
8
20
6
41
9
6
25
14
l-menthyl BINIM-DC
l-menthyl BINIM-DC
l-menthyl BINIM-DC
l-menthyl BINIM-DC CH3CH2CHCl2
l-menthyl BINIM-DC
l-menthyl BINIM-DC
l-menthyl BINIM-DM
l-menthyl BINIM-TC
l-menthyl BINIM-TM
l-menthyl
l-menthyl BINIM-TIP
l-menthyl BINIM-OH
Benzene
THF
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
BINIM-TB
a) The reaction was carried out in the presence of 1 mol% of the catalysts, which were prepared from
(R)-BINIMs and CuOTf•0.5C6H6, by adding 2 in a period of 6 h to 1 and then stirring was continued
for 16 h at room temperature. b) Determined by GC (Quadrex Bonded-Fused Silica). c) Determined
by GC after transformation into l-menthyl ester.
Table 2. Reactions of l-Menthyl Diazoacetate (1c) with Styrene (2)a)
Entry Copper Salt (Cat., mol%) Conc.b)/molL−1 Yield/% trans:cisc) % eec) trans
cis
1
2
3
4
5
6
7
8
9
CuOTf (1)
CuOTf (1)
CuOTf (2)
CuOTf (2)
1.1
81
92
93
92
94
96
92
92
92
82
83:17
85:15
90:10
85:15
87:13
82:18
87:13
86:14
86:14
71:29
57
62
68
55
67
57g)
65
65
62
14
43
84
81
63
76
85g)
82
83
89
2
0.55
0.55
0.55d)
0.55e)
0.55
0.28
0.55
0.55
0.55
CuOTf (2)
CuOTf (2)f)
CuOTf (2)
CuOTf (5)
[Cu(MeCN)4]PF6 (2)
Cu(OTf)2 (2)
10
a) The reaction was carried out in the presence of the catalysts, which were prepared from (R)-
BINIM-DC and copper salts, by adding the solution of 1c in CH2Cl2 to 2 in a period of 6 h and then
stirring was continued for 16 h at room temperature. See experimental section. b) The concentration
of 1c in CH2Cl2, which was added to 2 by a syringe pump. c) Determined by GC (Quadrex Bonded-
Fused Silica). The absolute configuration was determined as trans: (1S,2S), cis: (1S,2R) in compari-
son with the optical rotation reported. d) The reaction was carried out at 0 °C. e) The solution of 1c
was added in a period of 24 h and then the mixture was stirred for 22 h. f) (S)-BINIM-DC was used.
g) Absolute configuration; trans: (1R,2R), cis: (1R,2S).
studied (Scheme 1, Entries 9–14). As a result, the BINIM
l-menthyl diazoacetate (1c) (Entries 2, 3, and 7) compared
with the selectivity under the condition of Entry 1. In contrast,
the slow addition of a solution of diazoacetate 1c and lowering
the reaction temperature did not improve the enantioselectivity
(Entries 4 and 5). The amounts of the catalyst also did not sig-
nificantly affect the enantioselectivity (Entries 2, 3, and 8). In
the case of using the (S)-BINIM-DC instead of the (R)-
BINIM-DC, the enantioselectivity of the trans-adduct 3c was
slightly decreased, probably due to stereochemical mismatch-
ing between the (S)-catalyst and l-menthyl diazoacetate (1c)
(Entry 6). The use of easily handled [Cu(MeCN)4]PF6 as a
copper salt in asymmetric cyclopropanation instead of CuOTf
afforded a similar degree of enantioselectivity. However, the
use of Cu(OTf)2 as a copper salt showed an unsatisfactory re-
sult in terms of the enantioselectivities of both cyclopropanes.
This result was quite a contrast from Cu-bis(oxazoline)-cata-
containing 2,6-dicholorobenzylidene moieties gave the best re-
sult in terms of the enantioselctivity. Substitution of the para-
position on the benzene ring did not largely affect the enanti-
oselectivity in comparison to BINIM-DC and BINIM-DM
with BINIM-TC and BINIM-TM, respectively (Entries 3 vs
10 and 9 vs 11). Replacing the Cl by a larger Br, or isopropyl
groups on benzene rings, decreased the enantioselectivity as
well as the diastereoselectivity. These results suggest that not
only the size of the 2,6-substituents of the benzene ring, but
also the electronic character, influence the enantioselectivity.
From examinations of the amount of the catalyst, the con-
centration of the diazoacetate in CH2Cl2, and the addition time,
we found that the concentration greatly affected the enanti-
oselctivity (Table 2). Thus, the enantioselectivity was im-
proved especially for cis-adduct 4c by diluting the solution of

H. Suga et al.
Table 3. Reactions of l-Menthyl Diazoacetate (1c) with Other Olefinsa)
Bull. Chem. Soc. Jpn., 76, No. 1 (2003) 191
Entry
1
Olefin
Copper Salt
CuOTf
Temp/°C Products Yield/%
E:Zb)
% eeb)
E
Z
rt
rt
5, 6
7, 8
89
96
90:10
76
62
2
CuOTf
72:28c)
61c)
78c)
3
CuOTf
rt
9
69
—
74
4
5
6
7
8
CuOTf
CuOTf
CuOTf
[Cu(MeCN)4]PF6
[Cu(MeCN)4]PF6
0
9
9
9
9
9
75
80
83
80
71
—
—
—
—
—
90
95
98
93
96
−20
−40
rt
−20
9
[Cu(MeCN)4]PF6
[Cu(MeCN)4]PF6
rt
rt
10
11
82
43
—
—
96d)
94e)
10
11
12
CuOTf
CuOTf
rt
−20
12
12
66
60
—
—
65
58
13
[Cu(MeCN)4]PF6
rt
13
90
—
57
a) To a solution of Cu(Ⅰ)-(R)-BINIM-DC complex and olefin in CH2Cl2 was added l-menthyl diazoacetate (1c) in a
period of 6 h at the temperature cited in Table 1, and then the mixture was stirred at the same temperature for 16 h.
b) Determined by GC (Quadrex Bonded-Fused Silica). c) Determined by HPLC (Daicel Chiralpak AS). d) Deter-
mined by 1H NMR (500 MHz). e) Determined by HPLC (Waters Radial-pak 8NVC18 4µ).
increased by decreasing the temperature (Entry 4–6) and at
−40 °C the corresponding cyclopropane was obtained in high
chemical yield with 98% ee (Entry 6). When [Cu(MeCN)4]-
PF6 was used as a copper salt, a high level of enantioselectivity
(93% ee) was afforded, even at room temperature (Entry 7). It
is interesting to note that the cyclopropanation of 1,1-diphenyl-
ethylene with l-menthyl diazoacetate and d-menthyl diazoace-
tate proceeded only with 65% ee and 89% ee, respectively,
both in 55% yield using Ru(Ⅱ)-2,6-bis[(4S)-4-isopropyl-2-
oxazolin-2-yl]pyridine complex, which catalyzed the cyclo-
propanation of styrene with extremely high enantioselectivity
Scheme 2.
(up to 96% ee) in high yield.15 The high enantioselectivity of
the Cu(Ⅰ)-BINIM-DC-catalyzed reaction was not affected by
the electronic character of the substituent on the benzene ring
of 1,1-diarylethylenes (Entries 9 and 10).
lyzed asymmetric cyclopropanations, in which the use of
CuOTf and Cu(OTf)2 showed similar enantioselectivities.14
We applied the Cu(Ⅰ)-BINIM-DC complex to other olefins
(Scheme 2) under similar conditions of Entry 3 in Table 2
(Table 3). The reactions of 2-vinylnaphthalene (Entry 1), α-
methylstyrene (Entry 2), 2-methylpropene (Entries 11 and 12),
and methylenecyclohexane (Entry 13) showed moderate enan-
tioselectivities. On the other hand, it is noteworthy that the re-
actions of 1,1-diarylethylenes showed extremely high enanti-
oselectivities (up to 98% ee). The enantioselectivity of the
CuOTf-BINIM-DC-catalyzed cyclopropanation reaction of
1,1-diphenylethylene was quite dependent on the reaction tem-
perature. Although only 74% ee was observed under the con-
ditions at room temperature (Entry 3), the enantioselectivity
Model Study for Enantioselectivity in the Asymmetric
Cyclopropanation. In order to elucidate the reason for the
high enantioselectivity in Cu(Ⅰ)-BINIM-DC-catalyzed cyclo-
propanation reactions of 1,1-diarylethylenes, the structure of
the Cu(Ⅰ)-BINIM-DC-carbenoide complex was studied by a
PM3 calculation.16 The optimized structure of the complex is
shown in Figs. 1 and 2. From those views, the front side of the
carbenoide carbon adjacent to copper in Fig. 2 is relatively
more crowded by a 2,6-dichlorobenzylidene moiety than the
back side of the carbon. Therefore, the back side approach of
the olefin seems to be more accessible. If the phenyl group is

192 Bull. Chem. Soc. Jpn., 76, No. 1 (2003)
Cu(ꢀ)-BINIM-Catalyzed Asymmetric Reactions
Cl2 in the presence of 10 mol% chiral Cu(Ⅰ)-BINIM complex-
es (Table 4, Entries 1–5). Various catalysts were prepared by
mixing appropriate chiral BINIMs with [Cu(MeCN)4]PF6
(Scheme 3), followed by filtration under an argon atmosphere.
The corresponding 2-methoxycarbonyl-3-phenylaziridine 15
was produced in good-to-high yields. Among the chiral
ligands, the use of (R)-BINIM-DC showed the highest enanti-
oselectivity (75–77% ee), which was similarly observed in the
cyclopropanation reactions shown above. Although the azirid-
ination reactions were probably completed in less than 3 h, the
majority of the reactions were carried out for 19–20 h because
the disappearance of highly polar PhINTs (14) could not be
followed by TLC. In contrast to the Cu(Ⅱ)-bis(oxazoline)
complexes,10b it should be noted that the Cu(Ⅱ) complex,
which was prepared by Cu(OTf)2 and (R)-BINIM-DC under
similar conditions, did not catalyze the aziridination, and
therefore aziridine was not obtained.
Fig. 1. Optimized structure of the Cu(Ⅰ)-BINIM-DC com-
plex calculated by PM3.
oriented cis from the l-menthyloxycalbonyl group through this
approach, the steric hindrance between these groups may force
the back side approach much more easily. Hence, the high
enantioselctivities of the cyclopropanes derived from 1,1-
diarylethylenes and the cis-adduct of styrene can be obtained.
Aziridination Reactions of 3-Substituted Propenoate
and 1,3-Disubstituted 2-Propen-1-one Derivatives. Asym-
metric aziridination reactions of [N-(p-tolylsulfonyl)imino]-
phenyliodinane (PhINTs, 14) with methyl trans-cinnamate
(5 equiv) were initially examined at room temperature in CH2-
From an investigation of the reaction solvents, CH2Cl2 was
found to be the most effective solvent in terms of the yield and
enantioselectivity (Table 4, Entries 1 and 6–9). Using CHCl3
or CCl4, low or no yields of the aziridine were obtained, re-
spectively, which were probably attributable to the low solubil-
ity of PhINTs in these solvents (Entries 6 and 7). Interestingly,
Fig. 2. Proposed approach of 1,1-diphenylethylene.
Table 4. Enantioselective Aziridination of Methyl Cinnamatea)
Entry
Ligand
Solvent
Temp, Time
Yield/%
% eeb)
1
2
3
4
5
6
7
8
9
10
11
12
13
(R)-BINIM-DC
(R)-BINIM-DC
(R)-BINIM-TC
(R)-BINIM-TB
(R)-BINIM-TM
(R)-BINIM-DC
(R)-BINIM-DC
(R)-BINIM-DC
(R)-BINIM-DC
(R)-BINIM-DC
(R)-BINIM-DC
(R)-BINIM-DC
(R)-BINIM-DC
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CHCl3
CCl4
rt, 3 h
rt, 19 h
rt, 20 h
rt, 19 h
rt, 19 h
rt, 3 h
rt, 22 h
rt, 3 h
71
77
95
75
86
28
0
64
35
88
81
83
61
77
75
66
55
32
70
—
41
0
80
81
83
76
C6H6
MeCN
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
rt, 19 h
−20 °C, 1.5 h
−30 °C, 1.5 h
−45 °C, 2.5 h
−78 °C, 4 h
a) The reaction was carried out in the presence of 10 mol% of the catalyst, which was
prepared by mixing [Cu(MeCN)4]PF6 (11 mol%) and the ligand (10 mol%) for 1 h at
room temperature in the indicated solvent in this Table. b) Determined by HPLC using
Chiralpak AS (hexane:2-propanol = 9:1).

H. Suga et al.
Bull. Chem. Soc. Jpn., 76, No. 1 (2003) 193
conducting the reactions at lower temperatures of −20, −30,
and −45 °C (Entries 10–12, respectively) increased not only
the enantioselectivities, which improved to over 80% ee, but
also the overall yields. However, the reaction at −78 °C did
not improve the results in either yield or enantioselectivity. It
is noteworthy that, in terms of the reaction temperature, time,
and yield, the rate acceleration effects of this catalyst seemed
to be much higher than those of Cu(Ⅰ)-bis(oxazoline) com-
plexes10b and other reported catalysts without ligands, such as
CuClO4, [Cu(acac)2], and Cu(OTf)2.17
In an investigation of the trans-3-arylpropenoates, para-
substitution on the phenyl group, or a replacement of the phen-
yl group with 1-naphthyl or 2-naphthyl did not greatly affect
the enantioselectivities (Table 5, Entries 1–5). Satisfactory
enantioselectivities were observed regardless of the electron-
withdrawing or electron-releasing character of the para-sub-
stituents. However, replacing the aromatic group at the 3-posi-
tion by a hydrogen or a methyl group reduced the yields and
Scheme 3.
Table 5. Cu(Ⅰ)-BINIM-DC-Catalyzed Enantioselective Aziridinations of Olefinsa)
Entry
Olefin
Ligand
Temp, Time
Product Yield/%
% eeb)
Config.c)
1
2
3
X = Cl
X = CN (S)-BINIM-DC
X = Me
(R)-BINIM-DC
−20 °C, 22 h
−20 °C, 26 h
−20 °C, 75 h
16
17
18
82
69
41
81
(2S,3R)
(2R,3S)
(2R,3S)
90e)
83e)
(S)-BINIM-DC
4
5
6
7
(R)-BINIM-DC
(R)-BINIM-DC
(S)-BINIM-DC
(S)-BINIM-DC
−20 °C, 20 h
−20 °C, 25 h
rt, 24 h
19
20
21
22
74
74
13
30
77d)
68d)
36
(2S,3R)
(2S,3R)
NDf
rt, 18 h
43
NDf
8
(R)-BINIM-DC
−20 °C, 3 h
23
48
89
(2S,3R)
9
10
11
12
X = H
X = H
X = Cl
(R)-BINIM-DC
(R)-BINIM-DC
(S)-BINIM-DC
−20 °C, 3 h
−40 °C, 24 h
−20 °C, 23 h
−20 °C, 24 h
24
24
25
26
52
57
64
73
95
98
97
95
(2S,3R)
(2S,3R)
(2R,3S)
(2R,3S)g)
X = CN (S)-BINIM-DC
13
14
15
R = Ph
R = Ph
R = Me
(R)-BINIM-DC
(S)-BINIM-DC
(S)-BINIM-DC
−20 °C, 3 h
−40 °C, 24 h
−20 °C, 23 h
27
27
28
87
79
73
84e)
86e)
67e)
(2S,3R)g)
(2R,3S)g)
(2R,3S)g)
a) The reaction was carried out in the presence of 10 mol% of the catalyst, which was prepared by mixing
[Cu(MeCN)4]PF6 (10 mol%) and BINIM-DC (11 mol%) for 1 h at room temperature in CH2Cl2. b) Deter-
mined by HPLC using Chiralpak AS (hexane:2-propanol = 9:1). c) Absolute configurations were estab-
lished by the comparison of specific rotation with authentic sample. d) Determined by comparison of spe-
cific rotation with authentic sample (Ref. 2b). e) Determined by HPLC using Chiralpak AD (hexane:2-pro-
panol = 9:1). f) Not determined. g) Absolute configurations were tentatively assigned related to the adducts
of cinnamates.

194 Bull. Chem. Soc. Jpn., 76, No. 1 (2003)
Cu(ꢀ)-BINIM-Catalyzed Asymmetric Reactions
enantioselctivities (Entries 6 and 7). Therefore, aryl-substitu-
ents of the propenoate at the 3-position seem to play an impor-
tant role in appropriate enantiofacial selection.
ic substituents, but also trans-substituted carbonyl moieties on
the olefins, can play an important role in providing high enan-
tioselectivity of the Cu(Ⅰ)-BINIM-DC-catalyzed asymmetric
aziridinations.
We have observed that the size of the alkoxy moiety of the
cinnamate affected the enantioselectivity of the aziridination
reactions (Table 4, Entry 10; Table 5, Entries 8 and 9). In the
case of the aziridination of t-butyl trans-cinnamate under simi-
lar conditions at −40 °C (Table 5, Entry 10), enantioselectivity
was obtained with 98% ee in moderate yield. Reactions of t-
butyl 3-p-chloro- and 3-p-cyanophenylpropenoates also
showed extremely high enantioselectivity in good yields
(Entries 11 and 12). Under similar conditions, the 1,3-disub-
stituted 2-propen-1-one derivatives, trans-chalcone and trans-
benzylideneacetone (trans-4-phenyl-3-buten-2-one), also re-
acted in the presence of the chiral Cu(Ⅰ)-BINIM-DC catalyst
to give the corresponding aziridines in high yields with good
enantioselectivity (Entries 13–15). Similar to the 3-arylprope-
noates, the larger chalcone exhibited better enantioselectivity
than that of benzylideneacetone. Unfortunately, the corre-
sponding amido olefins, such as N-cinnamoylpyrrolidine and
3-cinnamoyl-2-oxazolidinone, did not react under those condi-
tions.
Although reactions of styrene and trans-β-methylstyrene
proceeded at −20 °C under similar conditions with high
yields, the enantioselectivities of the corresponding aziridines
were only 39% ee and 10% ee, respectively. It must be pointed
out that, in the presence of the Cu(Ⅰ)-(R)-BINIM-DC catalyst,
the absolute configuration of the phenyl-bearing carbon (S) in
the styrene adduct was opposite to those obtained from the 3-
arylpropenoates. These results suggested that not only aromat-
Model Study for Enantioselectivity in the Asymmetric
Aziridinations. The structure of the nitrenoid intermediate,
including the BINIM-DC ligand, was studied by semi-empiri-
cal molecular orbital calculations using the PM3 method.16
Following calculations of the singlet species, the two opti-
mised structures (Intermediates A and B) showed similar heat-
of-formation values (Fig. 3). For these intermediates, the
NSO2-moiety has both N,O-bidentate coordinations to the Cu-
diimine complex,27 as described in the hybrid density function-
al theory calculations, as reported by Norrby.18 The difference
between the two intermediates is that either of the two sulfonyl
oxygens can coordinate to the Cu-diimine complex. As shown
in Fig. 3, the front side around the nitrenoid nitrogen in both
intermediates A and B is shielded by the 2,6-dichlorophenyl
group. In contrast, the back side of the nitrenoid nitrogen
seems to be accessible, and it therefore seems that the ap-
proach of olefins from the backside is more facile. Since
trans/cis isomerization was not observed in the aziridinations
of trans-3-arylpropenoate and 1,3-disubstituted trans-2-pro-
pen-1-one derivatives, it is reasonable to consider a concerted
mechanism. A possible approach of the cinnamate is shown in
Fig. 4, in accordance with Norrby’s Cu-aziridine complex
model.18 In this approach, the enantioselectivity is explained
by the cleavage of the O–Cu of N,O-bidentate coordinations,
followed by the coordination of carbonyl oxygen with Cu and
the π-interaction of the 3-aryl group between the tosyl group.
Fig. 3. Optimized structure of intermediates A and B.
Fig. 4. Proposed approach of methyl cinnamate.

H. Suga et al.
Bull. Chem. Soc. Jpn., 76, No. 1 (2003) 195
99:1 v/v) to give 0.859 g (83% yield) of the corresponding cyclo-
propane.
Conclusions
Cyclopropanes 3a-c,15 4a-c,15 7,22, 23 8,22, 23 and 915, 22, 23 were
We have found that the chiral Cu(Ⅰ)-BINIM-DC complex is
an effective catalyst for asymmetric cyclopropanation and azir-
idination reactions. In the cyclopropanations, the reactions of
l-menthy diazoacetate with 1,1-diarylethylenes showed ex-
tremely high enantioselctivity (up to 98% ee). High levels of
enantioselectivity (up to 98% ee) were obtained in the aziridi-
nation reactions of 3-arylpropenoate and 1,3-disubstituted 2-
propen-1-one derivatives using PhIwNTs as a nitrene precur-
sor. Regarding model studies of the chiral carbene and nitrene
complexes optimised by a PM3 calculation, the high levels of
enantioselection could be explained by the proposed approach-
es (see Figs. 2 and 4). Experiments are currently underway to
evaluate the versatility of the chiral BINIM ligands in other
enantioselective reactions, such as Diels–Alder reactions25 and
1,3-dipolar cycloaddition reactions.
1
identified by comparisons of their H NMR signals with those
given in the literature. The trans:cis ratio and/or enantioselec-
tivity of cyclopropanes were determined by GC analysis using a
Quadrex Bonded-Fused Silica Capillary Column (0.25 mm i.d. ×
25 m × 0.25 µm) unless otherwise shown below. The E/Z ratio
and enantioselectivities of cyclopropanes 7 and 8 were determined
by an HPLC analysis (Daicel Chiralpak AS, hexane-i-PrOH 9:1
v/v, flow rate 1.0 mL/min).
l-Menthyl 2-naphthylcyclopropane-1-carboxylates (5 and 6)
were obtained as 90:10 mixture of trans- and cis-isomers. Color-
less solid; IR (KBr) 3420, 2952, 2927, 1717 (CwO), 1308, 1175
cm−1; [α]D24 = +7.6 ° (c 0.99, CHCl3).
l-Menthyl trans-2-Naphthylcyclopropane-1-carboxylate (5):
1H NMR (270 MHz, CDCl3) δ 0.77–2.05 (21H, m, CH, CH2,
CH3), 2.63–2.70 (1H, m, CH), 4.73 (1H, dt, J = 4.6, 10.9 Hz,
CO2CH), 7.18–7.81 (7H, m, Ar-H); 13C NMR (67.8 MHz, CDCl3)
δ 16.44, 17.07, 20.77, 22.01, 23.50, 24.34, 26.34, 31.38, 34.23,
40.96, 47.10, 74.50, 124.53, 124.69, 125.43, 126.22, 127.36,
127.59, 128.11, 132.23, 133.33, 137.66, 172.90.
Experimental
General. Melting points were determined on a Yanagimoto
melting-point apparatus and are uncorrected. IR spectra were
taken with a JASCO FT/IR-5300S spectrophotometer. 1H NMR
spectra were recorded on a JEOL JNM-MY60FT (60 MHz), a
JEOL GSX-400 (400 MHz), a JEOL GX-500 (500 MHz), or a
JEOL EX-270 instrument (270 MHz), and 13C NMR on a JEOL
GSX-400 or JEOL EX-270 spectrometer. Chemical shifts are ex-
pressed in parts per million downfield from tetramethylsilane as
an internal standard. MS spectra were measured with a HITACHI
M-80B mass spectrometer. Elemental analyses were performed
on aYanaco CHN recorder MT-3 or a Perkin-Elmer 2400 CHN re-
corder. High-performance liquid chromatography was measured
on a SHIMADZU LC-VP system. Optical rotations were record-
ed with a JASCO P-1010 polarimeter. For preparative column
chromatography, a Wakogel C-300 and a Silica gel 60 (Merck)
were employed. Medium-pressure liquid chromatography was
carried out using a column packed with Silica gel 60 (Merck, size
0.040–0.063 mm). All reactions were carried out under an argon
atmosphere in dried glassware.
Materials. All alkyl diazoacetates were prepared by a meth-
od described in the literature by Pfaltz.19 N-(p-Tolylsulfonyl)-
imino]phenyliodinane was prepared by the reported procedure.20
CuOTf•0.5C6H6 and Cu(OTf)2 were purchased from Tokyokasei
Co. [Cu(MeCN)4]PF6 was prepared by a method described in the
literature.21 Benzene, toluene, and THF were freshly distilled
from a sodium benzophenone ketyl still under argon. Dichlo-
romethane, chloroform, CH3CHCl2, and CH3CH2CHCl2 were pu-
rified by distillation, first from CaCl2, and then CaH2 under argon.
Acetonitrile was purified by distillation, first from P2O5, and then
CaH2 under argon.
l-Menthyl cis-2-Naphthylcyclopropane-1-carboxylate (6):
1H NMR (270 MHz, CDCl3) δ 0.22–1.60 (19H, m, CH, CH2,
CH3), 1.86 (1H, m, CH), 2.15 (1H, m, CH), 2.72 (1H, m, CH),
4.37 (1H, dt, J = 4.3, 10.6 Hz, CO2CH), 7.37–7.46 (3H, m, Ar-H),
7.70–7.78 (4H, m, Ar-H).
l-Menthyl 2,2-Diphenylcyclopropane-1-carboxylate (9):15, 22, 23
1
Colorless liquid; [α]D24 = +9.4° (c 0.86, CHCl3); H NMR (270
MHz, CDCl3) δ 0.65–1.80 (19H, m, CH, CH2, CH3), 2.17 (1H, dd,
J = 5.9, 5.0 Hz, CH), 2.55 (1H, dd, J = 7.9, 5.9 Hz, CH), 4.53
(1H, dt, J = 4.6, 10.9 Hz, CO2CH), 7.14–7.59 (10H, m, Ar-H).
l-Menthyl 2,2-Bis(4-methoxyphenyl)cyclopropane-1-carbox-
ylate (10): Colorless liquid; [α]D24 = +10.4° (c 0.80, CHCl3); IR
(Neat) 2954, 2869, 1727 (CwO), 1514, 1247, 1173, 1036 cm−1; 1H
NMR (270 MHz, CDCl3) δ 0.47–2.03 (19H, m, CH, CH2, CH3),
2.11 (1H, dd, J = 10.2, 4.6 Hz, CH), 2.46 (1H, t, J = 7.4 Hz, CH),
3.75 (6H, s, OCH3), 4.49 (1H, dt, J = 4.2, 10.2 Hz, CO2CH),
6.74–7.36 (8H, m, Ar-H); 13C NMR (67.8 MHz, CDCl3) δ 16.22,
20.09, 20.84, 22.03, 23.28, 25.82, 29.37, 31.27, 34.21, 38.45,
41.09, 46.85, 55.04, 55.26, 74.25, 113.61, 113.73, 128.51, 130.77,
132.46, 137.72, 158.05, 158.35, 170.30. The enantioselectivity
was determined by an HPLC analysis (Daicel Chiralpak AS, hex-
ane-i-PrOH 9:1 v/v, flow rate 1.0 mL/min). HRMS (EI) Found:
m/z 436.2602. Calcd for C28H36O4: M, 436.2615.
l-Menthyl 2,2-Bis(4-chlorophenyl)cyclopropane-1-carbox-
ylate (11): Colorless liquid; [α]D24 = +7.1° (c 0.97, CHCl3); IR
(Neat) 3445, 2956, 1718 (CwO), 1636, 1175, 1092 cm−1; 1H NMR
(270 MHz, CDCl3) δ 0.81–1.72 (19H, m, CH, CH2, CH3), 2.17
(1H, dd, J = 5.9, 5.3 Hz, CH), 2.52 (1H, dd, J = 8.3, 5.9 Hz, CH),
4.50 (1H, dt, J = 6.6, 10.9 Hz, CO2CH), 7.14–7.37 (8H, m, Ar-H);
13C NMR (67.8 MHz, CDCl3) δ 16.14, 20.01, 20.78, 21.99, 23.17,
25.82, 29.24, 31.22, 34.11, 38.35, 41.03, 46.76, 74.65, 128.61,
128.89, 131.11, 132.51, 133.08, 138.10, 142.95, 169.67. The
enantioselctivity was determined by 1H NMR (500 MHz). HRMS
(EI) Found: m/z 444.1668. Calcd for C26H30Cl2O2: M, 444.1625.
l-Menthyl 2,2-Dimethylcyclopropane-1-carboxylate (12):
Colorless crystals; [α]D24 = −2.4° (c 0.86, CHCl3); IR (KBr) 3437,
2954, 1713 (CwO), 1635, 1459, 1401, 1269, 1173, 1015 cm−1; 1H
NMR (270 Hz, CDCl3) δ 0.74–2.04 (27H, m, CH, CH2, CH3),
4.66 (1H, dt, J = 4.3, 10.9 Hz, CO2CH); 13C NMR (67.8 MHz,
General Procedure is Given for the Asymmetric Cyclopro-
panation Reaction of l-Menthyl Diazoacetate with 1,1-Diphenl-
ethylene. To a suspension of CuOTf•0.5C6H6 (14 mg, 0.055
mmol) in CH2Cl2 (5.0 mL) was added a solution of (R)-BINIM-
DC (35 mg, 0.058 mmol) in dry CH2Cl2 (7.5 mL) at room temper-
ature. Afer stirring for 1 h, 1,1-diphenyethylene (2.44 mL, 13.8
mmol) was added to the mixture. The mixture was cooled to −40
°C and a solution of l-menthyl diazoacetate (1c) (0.617 g, 2.75
mmol) in CH2Cl2 (5.0 mL) was added over a period of 6 h. The
mixture was stirred for 16 h, and then concentrated in vacuo. The
residue was chromatographed on silica gel (hexane–ethyl acetate,

196 Bull. Chem. Soc. Jpn., 76, No. 1 (2003)
Cu(ꢀ)-BINIM-Catalyzed Asymmetric Reactions
CDCl3) δ 16.38, 18.74, 20.79, 21.60, 22.07, 22.61, 23.49, 26.23,
26.96, 27.13, 31.43, 34.34, 41.35, 47.09, 73.97, 172.42. A satis-
factory analytical result was not obtained due to the instability of
12.
H, 4.53; N, 7.86%. Found: C, 60.60; H, 4.68; N, 7.78%. HPLC
(CHIRALPAK AS, 1:9 2-PrOH–hexane, flow rate = 0.5 mL/min,
Temp 35 °C, major = 139.1 min, minor = 154.0 min).
(2R,3S)-2-(Methoxycarbonyl)-3-(4-methylphenyl)-1-(p-tolyl-
sulfonyl)aziridine (18): Yellow oil; [α]D24 = +14.72° (c 0.84,
CHCl3); 83% ee; IR (neat) 3030, 2955, 2361, 2339, 1747 (CwO),
1597, 1518, 1494, 1442, 1402, 1336 (SO2), 1215, 1161 (SO2),
1-l-Menthyloxycarbonylspiro[2.5]octane (13):
Colorless
crystals; [α]D24 = −2.0° (c 0.97, CHCl3); IR (KBr) 3437, 2942,
1
2850, 1709 (CwO), 1445, 1403, 1172 cm−1; H NMR (270 Hz,
1
CDCl3) δ 0.75–1.71 (29H, m, CH, CH2, CH3), 1.89–2.05 (2H, m,
CH), 4.66 (1H × 78.5/100, dt, J = 4.3, 10.9 Hz, CO2CH), 4.68
(1H × 21.5/100, dt, J = 4.3, 10.9 Hz, CO2CH); 13C NMR (67.8
MHz, CDCl3) δ 16.37, 20.36, 20.80, 22.08, 23.48, 25.70, 25.77,
26.18, 26.22, 26.32, 26.41, 28.80, 31.42, 34.36, 37.44, 41.13,
47.08, 73.76, 172.31. A satisfactory analytical result was not ob-
tained due to the instability of 13.
1089, 1018, 935, 812, 783, 761, 721 cm−1; H NMR (60 MHz,
CDCl3) δ 2.33 (3H, s, Me), 2.42 (3H, s, Me), 3.38 (1H, d, J = 3.9
Hz, CH), 3.80 (3H, s, OMe), 4.34 (1H, d, J = 3.9 Hz, CH), 7.21–
7.88 (8H, m, Ar-H). Anal. Calcd for C18H19NO4S: C, 62.59; H,
5.54; N, 4.06%. Found: C, 62.75; H, 5.67; N, 3.79%. HPLC
(CHIRALPAK AS, 1:9 2-PrOH–hexane, flow rate = 0.5 mL/min,
Temp 35 °C, major = 75.8 min, minor = 35.6 min).
Typical Experimental Procedure for the Aziridination was
Exemplified by the Reaction of t-Butyl trans-Cinnamate. To
a suspension of [Cu(MeCN)4]PF6 (18 mg, 0.050 mmol) in CH2Cl2
(1.0 mL) was added (R)-BINIM-DC (33 mg, 0.055 mmol) in
CH2Cl2 (4.0 mL) at room temperature. After stirring for 1.5 h, the
mixture was filtered and washed with CH2Cl2 (6.0 mL) under an
argon atmosphere. To this mixture was added t-butyl trans-cin-
namate (510 mg, 2.5 mmol) and PhIwNTs (187 mg, 0.5 mmol)
successively. The mixture was stirred at −40 °C for 24 h, and
then filtered through a short plug of silica gel (2 × 5 cm). The
silica gel was washed with 50% hexane–ethyl acetate (100 mL),
and the filtrate was concentrated by rotary evaporation. The resi-
due was chromatographed over silica gel (hexane-AcOEt 6:1 v/v)
to give (2S,3R)-2-(t-butoxycarbonyl)-3-phenyl-1-(p-tolylsulfonyl)-
aziridine (24) (145 mg, 57%). The enantiomeric excess was deter-
mined as 98% ee by an HPLC analysis (Daicel Chiralpak AS).
Aziridine 15,10b 19,10b 20,10b 22,17 23,10b 24,11b and 2511b were
(2S,3R)-2-(Methoxycarbonyl)-3-(1-naphthyl)-1-(p-tolylsul-
fonyl)aziridine (19):10b Colorless solid; mp 49.0–50.0 °C; [α]D24
= +26.20° (c 1.03, CH2Cl2); 77% ee; IR (KBr) 3051, 2953, 2361,
1745 (CwO), 1597, 1510, 1439, 1392, 1336 (SO2), 1290, 1213,
1161 (SO2), 1087, 1037, 1018, 916, 802 cm−1; 1H NMR (60 MHz,
CDCl3) δ 2.41 (3H, s, Me), 3.60 (1H, d, J = 4.4 Hz, CH), 3.93
(3H, s, OMe), 4.95 (1H, d, J = 4.4 Hz, CH), 7.16–8.19 (11H, m,
Ar-H).
(2S,3R)-2-(Methoxycarbonyl)-3-(2-naphthyl)-1-(p-tolylsul-
fonyl)aziridine (20):10b Colorless solid; mp 105.5–106.8 °C;
[α]D24 = −8.76° (c 1.07, CHCl3); 68%; IR (KBr) 3040, 2953,
2359, 1745 (CwO), 1597, 1506, 1494, 1440, 1406, 1323 (SO2),
1
1240, 1205, 1161 (SO2), 1087, 1018 , 993 cm−1; H NMR (60
MHz, CDCl3) δ 2.40 (3H, s, Me), 3.65 (1H, d, J = 4.0 Hz, CH),
3.89 (3H, s, OMe), 4.59 (1H, d, J = 4.0 Hz, CH), 7.20–7.85 (11H,
m, Ar-H).
2-(Methoxycarbonyl)-3-methyl-1-(p-tolylsulfonyl)aziridine
(21): Yellow oil; [α]D23 = −3.86° (c 0.088, CHCl3); 36% ee; IR
(neat) 2955, 2361, 1747, 1683 (CwO), 1597, 1494, 1442, 1329
(SO2), 1244, 1161 (SO2), 1089, 1060, 970, 877, 817, 684 cm−1; 1H
NMR (60 MHz, CDCl3) δ 1.73 (1H, d, J = 5.6 Hz, Me), 2.43 (3H,
s, Me), 2.95–3.30 (1H, m, CH), 3.35 (1H, d, J = 4.1 Hz, CH),
7.32 (2H, d, J = 8.3 Hz, Ar-H), 7.86 (2H, d, J = 8.3 Hz, Ar-H).
HPLC (CHIRALPAK AS, 1:29 2-PrOH–hexane, flow rate = 0.5
mL/min, Temp 35 °C, major = 13.0 min, minor = 14.1 min). A
satisfactory analytical result was not obtained due to the instability
of 21.
1
identified by comparisons of their H NMR signals with those
given in the literature.
(2S,3R)-2-(Methoxycarbonyl)-3-phenyl-1-(p-tolylsulfonyl)-
aziridine (15):10b Pale yellow viscous oil; [α]D28 = −18.32° (c
0.18, CH2Cl2); 83% ee; IR (neat) 3056, 2955, 1747 (CwO), 1336
(SO2), 1161 (SO2) cm−1; 1H NMR (60 MHz, CDCl3) δ 2.48 (3H,
s, Me), 3.61 (1H, d, J = 4.1 Hz, CH), 3.95 (3H, s, OMe), 4.54
(1H, d, J = 4.1 Hz, CH), 7.43 (7H, s, Ar-H), 7.94 (2H, d, J = 7.3
Hz, Ar-H); HPLC (CHIRALPAK AS, 1:9 2-PrOH–hexane, flow
rate = 0.5 mL/min, Temp 35 °C, major = 48.6 min, minor = 71.6
min).
2-(Methoxycarbonyl)-1-(p-tolylsulfonyl)aziridine (22):17
Yellow oil; [α]D24 = −19.11° (c 0.736, CHCl3); 43% ee; IR (neat)
2957, 1748 (CwO), 1597, 1442, 1394, 1332 (SO2), 1292, 1232,
(2S,3R)-3-(4-Chlorophenyl)-2-(methoxycarbonyl)-1-(p-tolyl-
sulfonyl)aziridine (16): Colorless solid; mp 110.0–110.7 °C;
[α]D23 = −26.57° (c 1.35, CHCl3); 81% ee; IR (KBr) 2957, 1745
(CwO), 1597, 1494, 1444, 1369 (SO2), 1267, 1226, 1182, 1161
1
1163 (SO2), 1093, 1035, 908, 815, 781, 707, 692, 642 cm−1; H
NMR (60 MHz, CDCl3) δ 2.43 (3H, s, Me), 2.56 (1H, d, J = 3.9
Hz, one of CH2), 2.76 (1H, d, J = 7.1 Hz, one of CH2), 3.35 (1H,
dd, J = 7.1, 3.9 Hz, CH), 3.74 (3H, s, OMe), 7.32 (2H, d, J = 8.3
Hz, Ar-H), 7.84 (2H, d, J = 8.3 Hz, Ar-H). HPLC (CHIRALPAK
AD, 1:9 2-PrOH–hexane, flow rate = 0.5 mL/min, Temp 35 °C,
major = 44.0 min, minor = 42.1 min).
1
(SO2), 1087, 1012, 947, 837, 810, 792, 723, 672, 652 cm−1; H
NMR (60 MHz, CDCl3) δ 2.43 (3H, s, Me), 3.50 (1H, d, J = 3.9
Hz , CH), 3.86 (3H, s, OMe), 4.39 (1H, d, J = 3.9 Hz , CH), 7.25–
7.87 (8H, m, Ar-H). Anal. Calcd for C17H16ClNO4S: C, 55.81; H,
4.41; N, 3.83%. Found: C, 55.78; H, 4.49; N, 3.77%. HPLC
(CHIRALPAK AS, 1:19 2-PrOH–hexane, flow rate = 0.5
mL/min, Temp 35 °C, major = 56.7 min, minor = 85.5 min).
(2R,3S)-3-(4-Cyanophenyl)-2-(methoxycarbonyl)-1-(p-tolyl-
sulfonyl)aziridine (17): Colorless solid; mp 109.2–109.8 °C;
[α]D25 = +25.53° (c 0.79, CHCl3); 90% ee; IR (KBr) 3040, 2957,
2361, 2231 (CN), 1919, 1757 (CwO), 1597, 1506, 1444, 1425,
(2S,3R)-2-(Phenoxycarbonyl)-3-phenyl-1-(p-tolylsulfonyl)-
aziridine (23):10b Pale yellow viscous oil; [α]D24 = −51.75° (c
1.21, CHCl3); 89% ee; IR (neat) 3065, 3034, 2924, 2361, 1919,
1749 (CwO), 1653, 1595, 1493, 1456, 1417, 1338 (SO2), 1292,
1
1197 (SO2), 1087, 1026, 945, 869, 815, 748, 696, 599 cm−1; H
NMR (60 MHz, CDCl3) δ 2.42 (3H, s, Me), 3.69 (1H, d, J = 4.0
Hz, CH), 4.61 (1H, d, J = 4.0 Hz, CH), 7.33 (12H, s, Ar-H), 7.86
(2H, d, J = 8.6 Hz, Ar-H). HPLC (CHIRALPAK AS, 1:19 2-
PrOH–hexane, flow rate = 0.5 mL/min, Temp 35 °C, major =
48.3 min, minor = 45.0 min).
1402, 1329 (SO2), 1309, 1249, 1209, 1163 (SO2), 1109, 1086 cm−1
;
1H NMR (60 MHz, CDCl3) δ 2.44 (3H, s, Me), 3.47 (1H, d, J =
4.0 Hz, CH), 3.88 (3H, s, OMe), 4.48 (1H, d, J = 4.0 Hz, CH),
7.27–7.89 (8H, m, Ar-H). Anal. Calcd for C18H16N2O4S: C, 60.66;

H. Suga et al.
Bull. Chem. Soc. Jpn., 76, No. 1 (2003) 197
(2S,3R)-2-(t-Butoxycarbonyl)-3-phenyl-1-(p-tolylsulfonyl)-
aziridine (24):11b Pale yellow viscous oil; [α]D24 = −36.18° (c
1.13, CHCl3); 98% ee; IR (neat) 2980, 2361, 1738 (CwO), 1597,
1456, 1417, 1369 (SO2), 1338, 1240, 1161 (SO2), 1087, 929, 814,
763, 694, 594, 567, 441 cm−1; 1H NMR (60 MHz, CDCl3) δ 1.54
(9H, s, t-Bu), 2.42 (3H, s, Me), 3.41 (1H, d, J = 4.0 Hz, CH), 4.38
(1H, d, J = 4.0 Hz, CH), 7.34–7.28 (7H, m, Ar-H), 7.82 (2H, d, J
= 8.1 Hz, Ar-H). HPLC (CHIRALPAK AS, 1:19 2-PrOH-
hexane, flow rate = 0.5 mL/min, Temp 35 °C, major = 19.7 min,
minor = 21.5 min).
(2R,3S)-2-(t-Butoxycarbonyl)-3-(4-chlorophenyl)-1-(p-tolyl-
sulfonyl)aziridine (25):11b Colorless solid; mp 82.0–83.0 °C;
[α]D24 = +27.19° (c 0.56, CHCl3); 97% ee; IR (KBr) 2974, 2930,
1739 (CwO), 1597, 1496, 1435, 1400, 1371, 1332 (SO2), 1300,
1259, 1155 (SO2), 1089, 1014, 925, 875, 815, 723, 685 cm−1; 1H
NMR (60 MHz, CDCl3) δ 1.54 (9H, s, t-Bu), 2.42 (3H, s, Me),
3.38 (1H, d, J = 3.9 Hz, CH), 4.34 (1H, d, J = 3.9 Hz, CH), 7.21–
7.88 (8H, m, Ar-H). Anal. Calcd for C20H22ClNO4S: C, 58.89; H,
5.44; N, 3.43%. Found: C, 58.90; H, 5.44; N, 3.41%. HPLC
(CHIRALPAK AD, 1:29 2-PrOH–hexane, flow rate = 0.5 mL/
min, Temp 35 °C, major = 93.9 min, minor = 99.1 min).
(2R,3S)-2-(t-Butoxycarbonyl)-3-(4-cyanophenyl)-1-(p-tolyl-
sulfonyl)aziridine (26): Colorless solid; mp 44.5–45.0 °C; [α]D24
= +30.73° (c 1.07, CHCl3); 95% ee; IR (KBr) 3420, 2982, 2932,
2229, 1738 (CwO), 1597, 1433, 1396, 1369, 1338, 1307 (SO2),
1230, 1163 (SO2), 1116, 1087, 1018, 939, 815, 707, 690 cm−1; 1H
NMR (60 MHz, CDCl3) δ 1.55 (9H, s, t-Bu), 2.43 (3H, s, Me),
3.35 (1H, d, J = 4.2 Hz, CH), 4.41 (1H, d, J = 4.2 Hz, CH), 7.23–
7.89 (8H, m, Ar-H). Anal. Calcd for C21H22N2O4S: C, 63.30; H,
5.57; N, 7.03%. Found: C, 63.50; H, 5.59; N, 6.81%. HPLC
(CHIRALPAK AS, 1:19 2-PrOH–hexane, flow rate = 0.5 mL/
min, Temp 35 °C, major = 68.1 min, minor = 94.0 min).
(2R,3S)-2-Benzoyl-3-phenyl-1-(p-tolylsulfonyl)aziridine (27):
Yellow solid; mp 109.0–110.5 °C; [α]D25 = −4.65° (c 1.00,
CHCl3); 86% ee; IR (KBr) 3032, 2922, 2478, 2328, 1967, 1913,
1826, 1799, 1693 (CwO), 1597, 1450, 1323 (SO2), 1292, 1236,
1184, 1161 (SO2), 1099, 1082, 997, 947, 920, 846, 812, 744, 711
cm−1; 1H NMR (60 MHz, CDCl3) δ 2.40 (3H, s, Me), 4.28 (1H, d,
J = 4.4 Hz, CH), 4.52 (1H, d, J = 4.4 Hz, CH), 7.15–7.80 (14H,
m, Ar-H). Anal. Calcd for C22H19NO3S: C, 70.00; H, 5.07; N,
3.71%. Found: C, 70.07; H, 5.05; N, 3.55%. HPLC (CHIRAL-
PAK AD, 1:9 2-PrOH–hexane, flow rate = 0.5 mL/min, Temp 35
°C, major = 95.6 min, minor = 73.7 min).
(2R,3S)-2-Acetyl-3-phenyl-1-(p-tolylsulfonyl)aziridine (28):
Yellow oil; [α]D24 = −5.24° (c 0.85, CHCl3); 67%; IR (neat) 3065,
3034, 2924, 1716 (CwO), 1597, 1496, 1454, 1410, 1336 (SO2),
1240, 1205, 1159 (SO2), 1087, 929, 815, 744, 690 cm−1; 1H NMR
(60 MHz, CDCl3) δ 2.33 (3H, s, COMe), 2.42 (3H, s, Me), 3.73
(1H, d, J = 4.1 Hz, CH), 4.27 (1H, d, J = 4.1 Hz, CH), 7.20–7.80
(9H, m, Ar-H). Anal. Calcd for C17H17NO3S: C, 64.74; H, 5.43;
N, 4.44%. Found: C, 64.85; H, 5.49; N, 4.26%. HPLC
(CHIRALPAK AS, 1:9 2-PrOH–hexane, flow rate = 0.5 mL/min,
Temp 35 °C, major = 62.9 min, minor = 70.3 min).
(R)-N,Nꢀ-Bis(2,6-dichlorobenzylidene)-1,1ꢀ-binaphthyl-2,2ꢀ-
diamine ((R)-BINIM-DC). A suspension of MS 4A (3.2 mm
pellets, 12.0 g), (R)-1,1ꢀ-binaphthyl-2,2ꢀ-diamine (0.602 g, 2.12
mmol), and 2,6-dichlorobenzaldehyde (0.742 g, 4.24 mmol) in
benzene (18 mL) was stirred at room temperature for 16 h. After
MS 4A was removed by filtration, the filtrate was concentrated in
vacuo. The resulting solids were recrystallized from benzene-
hexane to give (R)-BINIM-DC (1.00 g, 79%): Yellow plate
(benzene-hexane); mp 216–218 °C; [α]D24 = −10.1° (c 0.96,
CH2Cl2); IR (KBr) 3051, 1636, 1615 (CwN), 1577, 1429, 814,
777, 748 cm−1; 1H NMR (270 MHz, C6D6) δ 6.17 (2H, t, J = 7.9
Hz, 4-H of 2,6-Cl2C6H3), 6.60 (4H, d, J = 7.9 Hz, 3-, 5-H of 2,6-
Cl2C6H3), 7.05–7.09 (2H, m, Ar-H), 7.19–7.22 (2H, m, Ar-H),
7.42 (2H, d, J = 8.6 Hz, Ar-H), 7.56 (2H, J = 8.3 Hz, Ar-H), 7.73
(2H, d, J = 7.9 Hz, Ar-H), 7.81 (2H, d, J = 8.6 Hz, Ar-H), 8.69
(2H, s, CHwN). Anal. Calcd for C34H20Cl4N2: C, 68.2; H, 3.37;
N, 4.68%. Found: C, 68.4; H, 3.52; N, 4.60%.
(R)-BINIM-TC, (R)-BINIM-TM, (R)-BINIM-DM, (R)-
BINIM-TB, and (R)-BINIM-TIP were prepared by the same pro-
cedure as (R)-BIMIN-DC.
(R)-N,Nꢀ-Bis(2,4,6-trichlorobenzylidene)-1,1ꢀ-binaphthyl-
2,2ꢀ-diamine ((R)-BINIM-TC): Yellow plates (diethyl ether–
hexane); mp 162.3–163.7 °C; [α]D24 = −5.9° (c 0.82, CH2Cl2); IR
(KBr) 3443, 1642, 1617 (CwN), 1573, 1540, 1504, 1361 cm−1; 1H
NMR (270 MHz, CDCl3) δ 7.16–8.00 (16H, m, Ar-H), 8.57 (2H,
s, CHwN). Anal. Calcd for C34H18Cl6N2: C, 61.20; H, 2.72; N,
4.20%. Found: C, 61.63; H, 2.91; N, 4.23%.
(R)-N,Nꢀ-Bis(2,4,6-trimethylbenzylidene)-1,1ꢀ-binaphthyl-
2,2ꢀ-diamine ((R)-BINIM-TM): Yellow prisms (benzene-hex-
ane); mp 191.5–193.0 °C; [α]D24 = −9.3° (c 0.99, CH2Cl2); IR
(KBr) 3051, 2965, 2917, 1629 (CwN), 1608, 1563, 808, 748 cm−1
;
1H NMR (270 MHz, CDCl3) δ 1.90 (12H, s, Me), 2.17 (6H, s,
Me), 6.67 (4H, s, Ar-H), 7.95–7.24 (12H, m, Ar-H), 8.68 (2H, s,
CHwN). Anal. Calcd for C40H36N2: C, 88.20; H, 6.66; N, 5.14%.
Found: C, 88.20; H, 6.74; N, 5.06%.
(R)-N,Nꢀ-Bis(2,6-dimethylbenzylidene)-1,1ꢀ-binaphthyl-2,2ꢀ-
diamine ((R)-BINIM-DM): Yellow prisms (diethyl ether-hex-
ane) mp 45.5–48.8 °C; [α]D24 = −4.3° (c 0.82, CH2Cl2); IR (KBr)
2954, 2912, 2359, 1685, 1614 (CwN), 1590, 1506, 1465, 1424
cm−1; 1H NMR (270 MHz, CDCl3) δ 1.92 (12H, s, Me), 6.84–7.98
(18H, m, Ar-H), 8.72 (2H, s, CHwN). Anal. Calcd for C38H32N2:
C, 88.3; H, 6.24; N, 5.42%. Found: C, 87.0; H, 6.51; N, 5.55%.
(R)-N,Nꢀ-Bis(2,4,6-tribromobenzylidene)-1,1ꢀ-binaphthyl-
2,2ꢀ-diamine ((R)-BINIM-TB): Yellow plates (benzene-hex-
ane); mp 102.0–104.0 °C; [α]D24 = +7.6° (c 0.99, CH2Cl2); IR
(KBr) 1616 (CwN), 1531, 1528, 1429, 1330, 856, 814, 735 cm−1
;
1H NMR (270 MHz, CDCl3) δ 7.26–8.00 (16H, m, Ar-H), 8.46
(2H, s, CHwN). Anal. Calcd for C34H18Br6N2: C, 43.73; H, 1.94;
N, 3.00%. Found: C, 43.65; H, 2.20; N, 2.83%.
(R)-N,Nꢀ-Bis(2,4,6-triisopropylbenzylidene)-1,1ꢀ-binaphthyl-
2,2ꢀ-diamine ((R)-BINIM-TIP): Yellow prisms (benzene-hex-
ane); mp 74.8–76.4 °C; [α]D24 = −15.1° (c 0.93, CH2Cl2); IR
(KBr) 2960, 2927, 2868, 1615 (CwN), 1591, 1459, 743 cm−1; 1H
NMR (270 MHz, CDCl3) δ 0.76 (12H, d, J = 6.9 Hz, Me of i-Pr),
0.92 (12H, d, J = 6.9 Hz, Me of i-Pr), 1.16 (12H, d, J = 6.9 Hz,
Me of i-Pr), 2.78–2.69 (6H, m, CH of i-Pr), 7.21–8.01 (16H, m,
Ar-H), 8.82 (2H, s, CHwN). Anal. Calcd for C52H60N2: C, 87.59;
H, 8.48; N, 3.93%. Found: C, 87.44; H, 8.51; N, 3.94%.
(R)-N,Nꢀ-Bis(2-hydroxybenzylidene)-1,1ꢀ-binaphthyl-2,2ꢀ-
diamine ((R)-BINIM-OH).
(R)-BINIM-OH was prepared
according to a procedure reported by Stack.24 A solution of 1,1ꢀ-
binaphthyl-2,2ꢀ-diamine (0.100 g, 0.35 mmol) and salicylaldehyde
(0.080 mL, 0.70 mmol) in ethanol (3.0 mL) was heated under re-
flux for 6 h. The resulting crystals were filtered and then recrys-
tallized from benzene-hexane to give (R)-BINIM-OH (0.152 g,
88%): Yellow plates (from benzene-hexane); mp 255–256.5 °C;
[α]D25 = +382.9° (c 0.16, CH2Cl2); H NMR (60 MHz, CDCl3) δ
1
6.63–8.19 (20H, m, Ar-H), 8.66 (2H, s, CHwN), 12.08 (2H, s,
OH); IR (KBr) 3440 (OH), 3053, 1609 (CwN), 1568, 1493, 1462,

198 Bull. Chem. Soc. Jpn., 76, No. 1 (2003)
Cu(ꢀ)-BINIM-Catalyzed Asymmetric Reactions
1283, 1196, 818 cm−1. Anal. Calcd for C34H24N2O2: C, 82.91; H,
4.91; N, 5.69%. Found: C, 83.18; H, 4.82; N, 5.41%.
9, 1 (1998). c) K. A. Jørgensen, M. Johannsen, S. Yao, H.
Audrain, and J. Thorhauge, Acc. Chem. Res., 32, 605 (1999). d) J.
S. Johnson and D. A. Evans, Acc. Chem. Res., 33, 325 (2000).
5
a) E. N. Jacobsen and M. H. Wu, In “Comprehensive
References
Asymmetric Catalyst,” ed by E. N. Jacobsen, A. Pfaltz, and H.
Yamamoto, Springer, Berlin (1999), Vol. 2, pp. 649–677. b) E. N.
Jacobsen, Acc. Chem. Res., 33, 421 (2000). c) M. J. Tokunaga, F.
Larrow, F. Kakiuchi, and E. N. Jacobsen, Science, 277, 936
(1997). d) T. Katsuki, Coord. Chem. Rev., 140, 189 (1995). e) T.
Katsuki, J. Mol. Cat., 113, 87 (1996).
1
a) R. Noyori, I. Tomino, M. Yamada, and M Nishizawa, J.
Am. Chem. Soc., 106, 6717 (1984). b) K. Narasaka, Synthesis,
1991, 1. c) D. Kaufmann and R. Boese, Angew. Chem., Int. Ed.
Engl., 29, 545 (1990). d) K. Mikami, M. Terada, and T. Nakai, J.
Am. Chem. Soc., 111, 1940 (1989). e) K. Mikami, M. Terada, and
T. Nakai, J. Am. Chem. Soc., 112, 3949 (1990). f) K. Mikami, S.
Narisawa, M. Shimizu, and M. Terada, J. Am. Chem. Soc., 114,
6566 (1992). g) K. Mikami, Y. Motoyama, and M. Terada, J. Am.
Chem. Soc., 116, 2812 (1994). h) K. Mikami and S. Matsukawa,
Nature, 385, 613 (1997). i) S. Kobayashi and H. Ishitani, J. Am.
Chem. Soc., 116, 4083 (1994). j) S. Kobayashi and M.
Kawamura, J. Am. Chem. Soc., 120, 5840 (1998). k) A. L. Costa,
M. G. Piazza, E. Tagaliavini, C. Trombini, and A. Umani-Ronchi,
J. Am. Chem. Soc., 115, 7001 (1993). l) M. Sibasaki, H. Sasai,
and T. Arai, Angew. Chem. Int. Ed., 36, 1236 (1997). m) M.
Bougauchi, S. Watanabe, T. Arai, H. Sasai, and M. Shibasaki, J.
Am. Chem. Soc., 119, 2329 (1997). n) T. Arai, H. Sasai, K.
Yamaguchi, and M. Shibasaki, J. Am. Chem. Soc., 120, 441
(1998). o) E. Emori, T. Arai, H. Sasai, and M. Shibasaki, J. Am.
Chem. Soc., 120, 4043 (1998). p) N. Yoshikawa, Y. M. A.
Yamada, J. Das, H. Sasai, and M. Shibasaki, J. Am. Chem. Soc.,
121, 4168 (1999). q) S. Matsunaga, J. Das, J. Roels, E. M. Vogl,
N. Yamamoto, T. Iida, K. Yamaguchi, and M. Shibasaki, J. Am.
Chem. Soc., 122, 2252 (2000). r) T. Nemoto, T. Ohshima, K.
Yamaguchi, and M. Shibasaki, J. Am. Chem. Soc., 123, 2725
(2001). s) N. Yoshikawa, N. Kumagai, S. Matsunaga, G. Moll, T.
Ohshima, T. Suzuki, and M. Shibasaki, J. Am. Chem. Soc., 123,
2466 (2001). t) T. Nemoto, T. Ohshima, and M. Shibasaki, J. Am.
Chem. Soc., 123, 9474 (2001). u) K. Ishihara, M. Kaneeda, and
H. Yamamoto, J. Am. Chem. Soc., 116, 11179 (1994). v) K.
Ishihara, S. Nakamura, M. Kaneeda, and H. Yamamoto, J. Am.
Chem. Soc., 118, 12854 (1996).
6
a) D. A. Evans, J. M. Janey, N. Magomedov, and J. S.
Tedrow, Angew. Chem., Int. Ed., 40, 1884 (2001). b) X. Zhou, J.
Huang, X. Yu, Z. Yhou, and C. Che, J. Chem. Soc., Dalton Trans.,
2000, 1075. c) I. P. Holmes, and H. B. Kagan, Tetrahedron Lett.,
41, 7457 (2000). d) X. Zhou, J. Huang, P. Ko, K. Cheung, M. C.
Chan, S. Peng, K. Cheung, and C. Che, J. Chem. Soc., Dalton
Trans., 1999, 3303. e) M. Cheng, M. C. Chan, S. Peng, K.
Cheung, and C. Che, J. Chem. Soc., Dalton Trans., 1997, 3479. f)
C. Ho, W. Cheng, M. Cheng, S. Peng, K. Cheng, and C. Che, J.
Chem. Soc., Dalton Trans., 1996, 405. g) K. Bernardo, S.
Leppard, G. Commenges, F. Dahan, and B. Meunier, Inorg.
Chem., 35, 387 (1996). h) D. D. Bernardo, A. Robert, F. Dahan,
and B. Meunier, New J. Chem., 19, 129 (1995).
7
A. Pfaltz, K. M. Lydon, M. A. McKervey, A. B. Charette,
and H. Lebel, In “Comprehensive Asymmetric Catalyst,” ed by E.
N. Jacobsen, A. Pfaltz, and H. Yamamoto, Springer, Berlin (1999),
Vol. 2, pp. 511–603; and references therein.
8
For the preliminary communication: H. Suga, T. Fudo, and
T. Ibata, Synlett, 1998, 933.
9
For a review: E. N. Jacobsen, In “Comprehensive Asym-
metric Catalyst,” ed by E. N. Jacobsen, A. Pfaltz, and H.
Yamamoto, Springer, Berlin (1999), Vol. 2, pp. 604–618.
10 Asymmetric aziridination using PhIwNTs: a) D. A. Evans,
K. A. Woerpel, M. M. Hinman, and M. M. Faul, J. Am. Chem.
Soc., 113, 726 (1991). b) D. A. Evans, M. M. Faul, M. T.
Bilodeau, B. A. Anderson, and D. M. Barnes, J. Am. Chem. Soc.,
115, 5328 (1993). c) Z. Li, K. R. Conser, and E. N. Jacobsen, J.
Am. Chem. Soc., 115, 5326 (1993). d) W. Zhang, N. H. Lee, and
E. N. Jacobsen, J. Am. Chem. Soc., 116, 425 (1994). e) Z. Li, R.
W. Quan, and E. N. Jacobsen, J. Am. Chem. Soc., 117, 5889
(1995). f) K. Noda, H. Hosoya, R. Irie, Y. Ito, and T. Katsuki,
Synlett, 1993, 469. g) H. Nishikori and T. Katsuki, Tetrahedron
Lett., 37, 9245 (1996). h) R. E. Lowenthal and S. Masamune, Tet-
rahedron Lett., 32, 7373 (1991). i) D. Tanner, P. G. Anderson, A.
Harden, and P. Somfai, Tetrahedron Lett., 35, 4631 (1994). j) A.
M. Harm, J. G. Knight, and G. Stemp, Synlett, 1996, 677. k) T.-S.
Lai, H.-L. Kwong, C.-M. Che, and S.-M. Peng, Chem. Commun.,
1997, 2373. l) M. J. Södergren, D. A. Alonso, and P. G.
Andersson, Tetrahedron: Asymmetry, 8, 3563 (1997). m) P.
Müller, C. Baud, Y. Jacquier, M. Moran, and I. Nägeri, J. Phys.
Org. Chem., 9, 341 (1996). n) R. S. Atkinson, W. T. Gattrell, A. P.
Ayscough, and T. M. Raynham, Chem. Commun., 1996, 1935.
Asymmetric aziridination usig chiral nitridomanganese complex-
es: o) S. Minakata, T. Ando, M. Nishimura, I. Ryu, and M.
Komatsu, Chem. Commun., 1998, 3392. p) M. Nishimura, S.
Minakata, T. Takahashi, Y. Oderaotoshi, and M. Komatsu, J. Org.
Chem., 67, 2101 (2002).
2
a) A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito,
T. Souchi, and R. Noyori, J. Am. Chem. Soc., 102, 7932 (1980). b)
R. Noyori, Chem. Soc. Rev., 18, 187 (1989). c) R. Noyori, Sci-
ence, 248, 1194 (1990). d) R. Noyori and H. Takaya, Acc. Chem.
Res., 23, 345 (1990). e) R. Noyori, CHEMTECH, 22, 360 (1992).
f) T. Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya, and R. Noyori,
J. Am. Chem. Soc., 117, 2675 (1995). g) T. Ohkuma, M. Koizumi,
H. Doucet, T. Pham, M. Kozawa, K. Murata, E. Kitayama, T.
Yokozawa, T. Ikariya, and R. Noyori, J. Am. Chem. Soc., 120,
13529 (1998). h) R. Noyori and T. Ohkuma, Angew. Chem., Int.
Ed., 40, 40 (2001). i) T. Ohkuma, M. Koizumi, K. Muňiz, G. Hilt,
C. Kabuto, and R. Noyori, J. Am. Chem. Soc., 124, 6508 (2002).
j) A. Yanagisawa, H. Nakashima, A. Ishiba, and H. Yamamoto, J.
Am. Chem. Soc., 118, 4723 (1996). k) A. Yanagisawa, Y.
Matsumoto, H. Nakashima, K. Asakawa, and H. Yamamoto, J.
Am. Chem. Soc., 119, 9319 (1997). l) F. Ozawa, A. Kubo, and T.
Hayashi, J. Am. Chem. Soc., 113, 1417 (1991). m) S. Yao, M.
Johannsen, R. G. Hazell, and K. A. Jørgensen, Angew. Chem. Int.
Ed., 37, 979 (1998). n) S. Oi, E. Terada, K. Ohuchi, T. Kato, Y.
Tachibana, and Y. Inoue, J. Org. Chem., 64, 8660 (1999).
11 After we repoted asymmetric cyclopropanation using
Cu(I)-BINIM-DC complex,8 the similar biaryldiimine-Cu(I) cata-
lyst for asymmetric aziridination was reported: a) C. J. Sanders, K.
M. Gillespie, D. Bell, and P. Scott, J. Am. Chem. Soc., 122, 7132
3
“Comprehensive Asymmetric Catalyst,” ed by E. N.
Jacobsen, A. Pfaltz, and H. Yamamoto, Springer, Berlin (1999).
a) A. Pfaltz, Acc. Chem. Res., 26, 339 (1993). b) A. K.
Ghosh, P. Mathivanan, and J. Cappiello, Tetrahedron: Asymmetry,
4

H. Suga et al.
Bull. Chem. Soc. Jpn., 76, No. 1 (2003) 199
Soc., 116, 2742 (1994).
18 P. Brandt, M. J. Södergren, P. G. Andersson, and P. Norrby,
J. Am. Chem. Soc., 122, 8013 (2000).
19 H. Fritschi, U. Leutenegger, and A. Pfaltz, Helv. Chem.
Acta, 71, 1553 (1988).
20 Y. Yamada, T. Yamamoto, and M. Okawara, Chem. Lett.,
1975, 361.
(2000). b) K. M. Gillespie, E. J. Crust, R. J. Deeth, and P. Scott,
Chem. Commun., 2001, 785. c) K. M. Gillespie, C. J. Sanders, P.
O’Shaunghnessy, I. Westmoreland, C. P. Thickitt, and P. Scott, J.
Org. Chem., 67, 3450 (2002). Very recently, Shi also reported the
aziridination reactions catalyzed by the CuClO4-BINIM-DC com-
plex: d) M. Shi, C.-J. Wang, and A. S. Chan, Tetrahedron: Asym-
metry, 12, 3105 (2001).
12 Parts of this work (Cu(I)-BINIM-DC-catalyzed aziridina-
tion reactions) was reported at the following meetings: a) 31st
Congress of Heterocyclic Chemistry, 1P-02, p.43 (2000). b) 79th
Meeting of the Chemical Society of Japan, 2H6 06, p. 1278
(2001).
21 G. J. Kubas, Inorg. Synth., 1997, 1990.
22 T. Aratani, Y. Yoneyoshi, and T. Nagase, Tetrahedron Lett.,
23, 685 (1982).
23 T. Ichiyanagi, M. Shimizu, and T. Fujisawa, Tetrahedron,
53, 9599 (1997).
13 The use of the other BINIMs, which were prepared from
(R)-1,1ꢀ-binaphthyl-2,2ꢀ-diamine with 2,6-dinitrobenzaldehyde, 9-
anthracenecarboxaldehyde, or 3,5-bis(benzyloxy)benzaldehyde,
showed less satisfactory results (enantioselectivities: <14% ee,
trans/cis < 65/35).
14 D. A. Evans, K. A. Woerpel, M. M. Hinman, and M. M.
Faul, J. Am. Chem. Soc., 113, 726 (1991).
15 a) H. Nishiyama, Y. Itoh, H. Matsumoto, S. Park, and K.
Itoh, J. Am. Chem. Soc., 116, 2223 (1994). b) H. Nishiyama, Y.
Itoh, Y. Sugawara, H. Matsumoto, K. Aoki, and K. Itoh, Bull.
Chem. Soc. Jpn., 68, 1247 (1995).
24 Y. Wang and T. D. P. Stack, J. Am. Chem. Soc., 118, 13097
(1996).
25 A part of the work has been already published: H. Suga, M.
Mitsuda, and A. Kakehi, Chem. Lett., 2002, 900.
26 Although diastereoselectivity may be a correct expression
in the reaction of l-menthyl diazoacetate, we described the diaste-
reoselectivity as enantioselevtivity in this paper because asymmet-
ric induction was mainly observed by the attribution of the chiral
Cu(Ⅰ)-BINIM-DC catalysts regardless of the configuration (see
Table 2, entry 3 vs 6).
27 In contrast, Scott reported that the density functional theo-
ry calculations of similar biaryldiimine-Cu(Ⅰ) catalytic intermedi-
ates did not locate N,O-bidentate coordinated structure.11b
16 Geometry optimizations were performed using PC Spartan
Pro (Version 1.0.5) program.
17 D. A. Evans, M. M. Faul, and M. T. Bilodeau, J. Am. Chem.