Asymmetric imidation of organic selenides into selenimides

Article abstract of DOI:10.1016/S0022-328X(00)00488-5

Treatment of aryl benzyl selenides with [N-(p-toluenesulfonyl)imino]phenyliodinane [TsN=IPh] in the absence or presence of copper(I) salt in toluene or acetonitrile affords the corresponding N-tosylselenimides in 31-46% yield. When the reaction is carried

Full text of DOI:10.1016/S0022-328X(00)00488-5

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 611 (2000) 475–487
Asymmetric imidation of organic selenides into selenimides
Yoshihiro Miyake, Masamitsu Oda, Arihiro Oyamada, Hiroya Takada, Kouichi Ohe,
Sakae Uemura *
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto Uni6ersity, Sakyo-ku, Kyoto 606-8501, Japan
Received 14 March 2000; accepted 26 March 2000
Abstract
Treatment of aryl benzyl selenides with [N-(p-toluenesulfonyl)imino]phenyliodinane [TsNꢀIPh] in the absence or presence of
copper(I) salt in toluene or acetonitrile affords the corresponding N-tosylselenimides in 31–46% yield. When the reaction is
carried out in the presence of optically active 4,4%-disubstituted bis(oxazoline) as a ligand together with molecular sieves,
enantioselective imidation occurs to give optically active N-tosylselenimides and the best result is obtained from benzyl 2-naphthyl
selenide (64% yield and 36% ee). Similar treatment of allylic selenides gives the corresponding optically active allylic amides (up
to 71% yield and 30% ee). In the case of diastereoselective imidation, the reaction of diaryl selenides bearing a chiral oxazolinyl
moiety with TsNꢀIPh or Chloramine–T trihydrate [TsN(Cl)Na·3H2O] has been successfully carried out to give the corresponding
optically active N-tosylselenimides in good yields (up to 97% isolated yield and 76% de). The absolute configuration around the
selenium atom of (4S)-Se-[2-(4-isopropyloxazolin-2-yl)phenyl]-Se-phenyl-N-(p-toluenesulfonyl)selenimide [(4S)-13], obtained by
diastereoselective imidation of the corresponding selenide with Chloramine–T trihydrate, has been determined to be S by X-ray
crystallographic analysis, from the result of which an ionic reaction pathway involving a chloroselenonium ion intermediate is
proposed. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Asymmetric imidation; Organic selenides; Organic selenimides; Chloramine–T trihydrate; [N-(Tosyl)imino]phenyliodinane
but the scope of this reaction has not been fully devel-
oped, probably because of low yields of the products as
1. Introduction
well as their quite low optical activity [5]. Koizumi et al.
attempted the transformation of optically pure alkoxy-
chloroselenuranes, prepared by chlorination of optically
active selenides having the 2-exo-hydroxy-10-bornyl
group as a chiral auxiliary with tert-butyl hypochlorite,
to the corresponding N-tosylselenimides by treatment
with N-tosylamine chloride, but they could not isolate
the expected selenimide [6]. Very recently, Kamigata
and co-workers have shown examples of (i) the conver-
sion of an optically active selenoxide, obtained by
optical resolution of a diastereomeric mixture, into the
corresponding enantiomerically pure organic selenimide
and (ii) the conversion of racemic organic selenimides
into the corresponding enantiomerically pure organic
selenimides by optical resolution, and ascertained
the detailed stereochemistry of these compounds
[7]. We have already demonstrated the diastereo-
selective imidation of chiral cinnamyl 2-(1-dimethyl-
aminoethyl)ferrocenyl selenide using TsNꢀIPh or
The chemistry of chiral sulfoxides, sulfonium ylides,
and sulfimides has been investigated with a good deal
of success [1]. In this field, we also succeeded in the
synthesis of optically active organosulfur compounds
[2]. In contrast, the asymmetric synthesis of analogous
organoselenium compounds has been limited [3]. We
have already demonstrated the asymmetric induction to
several organoselenium compounds to afford chiral or-
ganic selenoxides which lead to optically active com-
pounds by the successive selenoxide elimination and
[2,3] sigmatropic rearrangement [4]. Compared to the
chemistry of chiral organic selenoxides, that of organic
selenimides, N-analogous to the selenoxides, has been
much less studied. In 1981, Krasnov et al. reported the
first synthesis of the optically active organic selenimides
starting from dialkyl- and diaryl-selenium dichloride,
* Corresponding author. Fax: +81-75-753-3573.
E-mail address: uemura@scl.kyoto-u.ac.jp (S. Uemura).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00488-5

476
Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
Chloramine–T [TsN(Cl)Na] as imidation reagents to
produce the optically active allylic amine derivatives [8].
However, the direct synthesis of chiral organic selen-
imides from the corresponding selenides has not yet
been reported. We report here the results of the direct
enantioselective and diastereoselective imidation of var-
ious organic selenides into the corresponding chiral
organic selenimides in detail [9] and also propose the
reaction pathway of diastereoselective imidation by
considering the absolute configuration of the obtained
diaryl selenimide.
sylselenimides (Eq. (1)). We have already reported that
the direct catalytic imidation of prochiral organic
sulfides to the corresponding optically active N-tosyl-
sulfimides proceeded with TsNꢀIPh in the presence of
CuOTf and bis(oxazoline) in various solvents [2c–f].
Since the combination of Cu(I) salt and bis(oxazoline)
was necessary for asymmetric imidation, we first looked
for the solvent in which the imidation of prochiral
selenides 1 with TsNꢀIPh did not proceed in the ab-
sence of CuOTf. Treatment of benzyl phenyl selenide
(1a) with TsNꢀIPh in MeCN and CH2Cl2 at 25°C for
24 h afforded benzyl phenyl N-tosylselenimide (3a) in
46% yield and in a trace amount, respectively, but in
toluene no reaction occurred (Table 1, entries 2 and 3
versus 4).
2. Results and discussion
2.1. Catalytic enantioselecti6e imidation of prochiral
organic selenides
First, we describe the first example of the direct
catalytic enantioselective imidation of prochiral organic
selenides into the corresponding optically active N-to-
(1)
Table 1
Effect of solvent on imidation of benzyl phenyl selenide 1a a
Therefore, we chose toluene as solvent [10] and car-
ried out imidation of 1a with TsNꢀIPh in the presence
of CuOTf (10 mol%) and the optically active bis(oxazo-
line) 2 (12 mol%) at 25°C for 24 h under N2 [11]. The
N-tosylselenimide 3a was formed in 40% yield, but the
expected asymmetric induction did not occur. However,
further studies revealed that the reaction proceeded
enantioselectively when molecular sieves were added to
a reaction mixture (Eq. (1); compare entry 1 with entry
2 in Table 2). This is probably due to the interference of
the rapid selenimide–selenoxide equilibrium (Scheme 1)
by removal of water present in the reaction mixture
[12]. Rapid racemization of the selenoxide is well
known (Scheme 2, (a) and (b)) [13]. The rearrangement
of selenurane intermediate into a stable selenurane [14]
by means of pseudorotation has also been reported
(Scheme 2, (c)) [12,15].
Entry
Solvent
Time (h)
3a yield (%)
1
2
3
CH3CN
CH3CN
CH2Cl2
Toluene
Toluene
2
24
24
24
24
7
46
trace
0
4
5 b
31
a All reactions were performed in solvent (0.02 M) at 25°C using
selenide (1a) (0.2 mmol) and TsNꢀIPh (0.1 mmol).
b CuOTf (0.01 mmol, 10 mol%) was added.
Table 2
Catalytic enantioselective imidation of selenides 1 a
Entry
Substrate
Product
Yield (%) b
ee (%) c
1 d
2
1a
1a
1a
1b
1c
1d
1e
1f
3a
3a
3a
3b
3c
3d
3e
3f
40
53
18
37
23
64
0
32
33
20
29
36
3 e
4
At a lower temperature the reaction was slower (en-
try 3). The reaction also proceeded with several other
aryl benzyl selenides. In the case of methyl phenyl
selenide (1e) the reaction proceeded, but the corre-
sponding N-tosylselenimide 3e, the formation of which
5
6 f
7
Not isolated
No reaction
No reaction
8
9
1g
3g
1
was determined by H-NMR spectral analysis of the
a All reactions were performed in toluene (0.02 M) at 25°C in the
presence of 12 mol% chiral ligand 2, 10 mol% CuOTf and MS 3A for
crude product, could not be isolated because of decom-
position to the corresponding selenoxide. Selenides hav-
24 h unless otherwise noted.
b Isolated yield.
c Enantiomeric excesses were determined by HPLC using suitable
chiral columns.
d Without MS3A.
e At 0°C.
f MS4A was added, for 48 h.
Scheme 1.

Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
477
2.2. Diastereoselecti6e imidation of chiral diaryl
selenides
We have already reported that the diastereoselective
sulfimidation of various diaryl sulfides having a chiral
auxiliary to the corresponding N-tosylsulfimides pro-
ceeded with NTs sources in the presence of copper salts
[16]. We describe here the selenium version of this
reaction, namely, the direct diastereoselective imidation
of diaryl selenides having a chiral auxiliary into the
corresponding optically active N-tosylselenimides (Eqs.
(3) and (4)).
The optically active chiral organic selenides 7–10
were prepared by methods similar to those reported by
Williams et al. as shown in Schemes 3 and 4 [17]. After
(1S,2S)-(+)-2-amino-1-phenyl-1,3-propanediol-derived
oxazoline was protected as its silyl ether, it was ortho-
lithiated and then quenched with the corresponding
diaryl diselenides to produce diaryl selenides (4S,5S)-
7a–7d. Subsequently, the silyl protecting group was
removed to give (4S,5S)-8 and then it was converted to
diaryl selenide (4S,5S)-9 by methylation of a hydroxyl
group (Scheme 3). On the other hand, diaryl selenide
Scheme 2.
ing bulky substituents on an aryl ring such as benzyl
2,4,6-tri-tert-butylphenyl selenide (1f) did not react at
all. To make clear the absolute configuration of the
produced selenimides, we tried to synthesize the selen-
imide 3g, the absolute configuration of which is known
[7b], but the diaryl selenide 1g did not react at all under
the present reaction conditions. Typical results are
shown in Table 2.
When this reaction was applied to various allyl aryl
selenides 4, the expected chiral allylic N-tosylamides 6a
and 6b (up to 30% ee) were obtained in moderate to
good yields via [2,3] sigmatropic rearrangement of the
initially produced chiral allylic N-tosylselenimide 5 (Eq.
(2), Table 3). This result clearly shows that the chirality
transfer occurred at the rearrangement step.
(4S)-10 bearing an
L-valinol-derived oxazolinyl moiety
was prepared by condensation of benzonitrile with
L
-
valinol followed by lithiation of the benzene ring and
quenching with diphenyl diselenide (Scheme 4).
On treatment of the selenide (4S,5S)-7a with
TsNꢀIPh in acetonitrile or toluene, both the product
yield and the asymmetric induction were improved
using a copper salt (10 mol%) as catalyst and the
corresponding optically active N-tosylselenimides
(4S,5S)-11a were obtained in 77–92% yield with mod-
erate diastereoselectivity (up to 41% de) as shown in
Eq. (3), Table 4 (entries 1–6). Unfortunately, a lower
Table 3
Catalytic enantioselective imidation of allylic selenides 4 a
(2)
Entry
Substrate
R1
R2
Product
Yield (%) b
ee (%) c
1
2
3
4
5
6
7
4a
4b
4c
4d
4e
4f
Ph
Ph
Ph
Ph
Ph
Me
Me
Ph
6a
6a
6a
6a
6a
6b
6b
63
35
71
52
Trace
34
20
17
28
30
–
Ferrocenyl
1-Naphthyl
2-Naphthyl
2-NO2C6H4
Ph
8 d
17 d
4g
2-Naphthyl
53
a All reactions were performed in toluene (0.02 M) in the presence of 12 mol% chiral ligand 2, 10 mol% CuOTf and MS3A for 24 h.
b Isolated yield.
c Enantiomeric excesses were determined by HPLC using Daicel Chiralcel OD column unless otherwise noted.
d Enantiomeric excesses were determined by 1H-NMR analysis in the precence of Eu(hfc)3.

478
Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
Scheme 3.
Scheme 4.
Table 4
Diastereoselective imidation of organic selenides using TsNꢀIPh a
(3)
Entry
(4S,5S)-Selenide
R
Catalyst
Solvent
Product
Yield (%) b
de (%) c
1
2
3
4
5
6
7
7a
7a
7a
7a
7a
7a
9
SiMe2But
SiMe2But
SiMe2But
SiMe2But
SiMe2But
SiMe2But
Me
None
CH3CN
CH3CN
CH3CN
Toluene
Toluene
Toluene
CH3CN
11a
11a
11a
11a
11a
11a
12
42
92
83
42
79
77
91
17
41
41
13
41
38
11
CuOTf
Cu(OTf)2
None
CuOTf
Cu(OTf)2
CuOTf
a All reactions were performed in solvent (0.20 M) at 25°C using selenide (0.20 mmol), TsNꢀIPh (0.24 mmol), catalyst (0.02 mmol), MS4A for
24 h.
b Isolated yield.
c The value was determined by 1H-NMR spectroscopy.
tions to (4S,5S)-7b, 7c and 7d, in which the substituent
was introduced to the ortho-position of the phenyl
group of (4S,5S)-7a (entries 2, 7–9). In the case of
(4S,5S)-7b, the reaction proceeded with better
diastereoselectivity, the product being (4S,5S)-11b,
whereas the use of (4S,5S)-7c gave only a trace amount
of the corresponding selenimide (4S,5S)-11c (entries 7
and 8). On the contrary, a slightly lower diastereoselec-
tivity (53–55% de) was observed on treatment of
stereoselectivity was obtained from the selenide
(4S,5S)-9, the products being (4S,5S)-12 (entry 7).
On the other hand, when commercially available
Chloramine–T trihydrate [TsN(Cl)Na·3H2O] was em-
ployed as an NTs source in toluene in the presence of
copper salt, a better result in stereoselectivity was ob-
tained (Eq. (4), Table 5 (entry 1)). Further studies
revealed that a similar result was obtained even in the
absence of a copper salt in a variety of solvents except
acetonitrile (entries 2–6). Hoping to obtain better
diastereoselectivity, we applied these reaction condi-
(4S,5S)-diaryl selenides such as
9 and 10 with
TsN(Cl)Na·3H2O in toluene, where the substituent at

Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
479
the 4-position of the oxazoline ring was
a
and 14b. Then, the replacement of the dissociative
chlorine atom on the selenium of 14b with the N-tosyl-
amine anion occurs retentively to give the product in
which the configuration around selenium atom is S [6].
From the X-ray analysis, we recognized the distance
methoxymethyl group or an isopropyl group, the prod-
ucts being (4S,5S)-12 and 13, respectively (entries 10
and 11).
In order to determine the absolute configuration of
the produced N-tosylselenimides, we tried to obtain a
single crystal of a single diastereoisomer of (4S)-13
from the diastereomeric mixture of 53% de by means of
recrystallization from n-hexane–CH2Cl2. The molecu-
lar structure was clarified by X-ray analysis. As shown
in an ORTEP drawing (Fig. 1), the major N-tosylselen-
imide of the present imidation was revealed to have an
absolute configuration of 4S,SSe ([h]2D5= −161.8; c 0.22
in CHCl3). In analogy with (4S,SSe)-13, the absolute
configuration around the selenium atom of the major
N-tosylselenimides 11a, 11b, 11d and 12 might be as-
signed to S.
A plausible reaction pathway of the diastereoselective
imidation of (4S)-10 is shown in Scheme 5. This path-
way is different from that proposed in the imidation of
organic sulfides in which the presence of copper salt is
necessary for the reaction and therefore the presence of
an intermediate having a coordination between Cu, S
and N was assumed [16]. First, the selenium of 10
attacks the chlorine atom of N-tosylamine chloride
[H(Cl)NTs] produced by the hydrolysis of Chloramine–
T [18] to afford chloroselenonium ion intermediates 14a
,
(2.68 A) between Se and N of the oxazoline ring, which
was shorter than the sum of van der Waals radii of Se
,
and N (3.45 A) [19]. This result suggests the existence of
Se···N interaction, as has been reported [20], which
might affect the stereochemistry of the replacement [21].
We have revealed the effectiveness of optically active
diaryl sulfides and sulfimides having a chiral oxazolinyl
moiety (sulfur version of 9, 11a and 12) as chiral
ligands in the Pd-catalyzed allylic substitution [16]. In
view of synthetic application of the produced selenides
and N-tosylselenimides containing an oxazolinyl group,
we have now attempted to use these compounds as
chiral ligands in asymmetric reactions (Eqs. (5) and
(6)). The results of the use of 7a, 8, 9 and 11a as chiral
ligands in the Pd-catalyzed allylic alkylation of 1,3-
diphenyl-3-acetoxy-1-propene with dimethyl malonate
are summarized in Table 6. A good enentioselectivity
was obtained, but unfortunately the chemical yield was
quite low. The application of these compounds as chiral
ligands in Rh-catalyzed hydrosilylation of ketones with
diphenyl silane [22] resulted in a very low stereoselectiv-
ity with moderate chemical yields (Eq. (6), Table 7).
Table 5
Diastereoselective imidation of organic selenides using TsN(Cl)Na·3H2O a
(4)
Entry
(4S,5S)-Selenide
Ar
R1
R2
Solvent
Product
Yield (%) b
de (%) c
1 d
2
3
4
5
6
7
8
9
7a
7a
7a
7a
7a
7a
7b
7c
7d
9
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
H
CH2OSiMe2But
CH2OSiMe2But
CH2OSiMe2But
CH2OSiMe2But
CH2OSiMe2But
CH2OSiMe2But
CH2OSiMe2But
CH2OSiMe2But
CH2OSiMe2But
CH2OMe
Toluene
Toluene
CH3CN
Cyclohexane
Et2O
11a
11a
11a
11a
11a
11a
11b
11c
11d
12
80
92
68
40
83
69
64
Trace
75
92
60
67
9
60
63
47
76
–
THF
2,4,6-Me3C6H2
2,4,6-Pri3C6H2
2-MeOC6H4
Ph
Toluene
Toluene
Toluene
Toluene
Toluene
30
55
53
10
11
10
Ph
Pri
13
97
a All reactions were performed in solvent (0.20 M) at 25°C using selenide (0.20 mmol), TsN(Cl)Na·3H2O (0.24 mmol), catalyst (0.02 mmol),
MS4A for 24 h.
b Isolated yield.
c The value was determined by 1H-NMR spectroscopy.
d Cu(OTf)2 (0.02 mmol, 10 mol%) was added.

480
Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
,
Fig. 1. Crystal structure of the N-tosylselenimide (4S,SSe)-13. Selected bond lengths (A) and angles (°): Se(1)–N(2), 1.805(5); Se(1)–C(1), 1.969(7);
Se(1)–C(13), 1.937(8); N(2)–Se(1)–C(1), 100.4(3); N(2)–Se(1)–C(13), 96.7(3); C(1)–Se(1)–C(13), 97.5(3).
Scheme 5.
3. Conclusion
tained by imidation of the corresponding selenide with
Chloramine–T trihydrate, was determined to be S by
X-ray crystallographic analysis. In the diastereoselective
imidation with Chloramine–T trihydrate, an ionic reac-
tion scheme involving a chloroselenonium ion interme-
diate is proposed.
Although the enantioselectivity and diastereoselectiv-
ity obtained in the imidation of organic selenides are
not yet satisfactory (up to 36% ee and 76% de) and are
lower than for the corresponding sulfur case [2c–f], the
findings presented here are (i) the first example of the
direct catalytic enantioselective imidation of organic
selenides into the corresponding optically active selen-
imides, and also (ii) the first example of the direct
imidation of diaryl selenides having a chiral auxiliary
into the corresponding optically active selenimides. The
absolute configuration around the selenium atom of the
isolated diastereomerically pure selenimide (4S)-13, ob-
4. Experimental
1H- and 13C-NMR spectra were measured on JEOL
EX-400, JEOL JNM-AL300 and JEOL JNM-GSX270
spectrometers for solutions in CDCl3 with Me4Si as an
internal standard. The following abbreviations are

Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
481
Table 7
used: s singlet, d doublet, sep septet, m multiplet. IR
Enantioselective Rh-catalyzed hydrosilylation a
spectra were recorded with a Nicolet Impact 400D
FT-IR spectrometer. Analytical thin layer chro-
matographies (TLC) were performed with silica gel 60
Merck F-254 plates. Column chromatography on silica
gel was performed with Cica-Merck silica gel 60. Melt-
ing points are uncorrected. GLC analyses were carried
out with a Shimadzu GC-14A instrument equipped
with a 5% OV-17 on Chromosorb W column (glass
column, 3 mm×2 m) and a Shimadzu GC-14B instru-
ment equipped with a Chiraldex G-TA column (TCI,
fused silica capillary column, 0.25 mm×30 m, 0.125
mm film thickness). GLC yields were determined using
pentamethylbenzene as an internal standard. HPLC
analyses were carried out on a D-7500 instrument
(Hitachi) with an L-7400 detector at 40°C. Optical
rotations were measured on a Jasco DIP-1000 instru-
ment. High-resolution mass spectra (HRMS) were ob-
(6)
Entry
Ligand
Yield (%) b
ee (%) c
1
2
3
4
(4S,5S)-7a
(4S,5S)-9
(4S,5S)-11a
(4S,5S)-12
70
35
43
40
1
1
6
1
a Acetophenone (1.0 mmol), catalyst (0.0025 mmol), ligand (0.0050
mmol), Ph2SiH2 (1.35 mmol), rt, 20 h.
b GLC yield.
c The value was determined by GLC.
4.1. Typical procedure for asymmetric catalytic
imidation of aryl benzyl selenides
To a solution of MS3A (ca. 300 mg), CuOTf (2.5 mg,
0.010 mmol) and chiral bis(oxazoline) 2 (4.0 mg, 0.012
mmol) in 5.0 ml of toluene were added first TsNꢀIPh
(37.3 mg, 0.10 mmol) and then the selenide (0.20
mmol), and the resulting mixture was stirred under
nitrogen at 25°C for 24 h. Removal of the precipitates
from the mixture through Celite and evaporation of the
solvent gave a crude product. Purification by silica gel
column chromatography gave a pure selenimide. Enan-
tiomeric excesses were determined by HPLC using a
suitable chiral column as shown below.
tained with
a JEOL JMS-SX102A spectrometer.
Elemental analyses were performed at the Microanalyt-
ical Center of Kyoto University. Tetrahydrofuran
(THF) and diethyl ether (Et2O) were distilled from
sodium
benzophenone
ketyl
under
argon.
Dichloromethane (CH2Cl2) was distilled from calcium
hydride. Toluene, acetonitrile (CH3CN) and cyclohex-
ane were distilled from P2O5 just before use. Chlo-
ramine–T
(1S,2S)-(+)-2-amino-1-phenyl-1,3-propanediol, (R)-
(+)-2,2%-isopropylidenebis(4-phenyl-2-oxazoline) (2)
and Eu(hfc)3 were commercial products. -Valinol was
prepared from -valine according to the reported
trihydrate,
CuOTf,
Cu(OTf)2,
L
4.1.1. Se-Benzyl-Se-phenyl-N-(p-toluenesulfonyl)-
selenimide (3a)
L
method [23]. 1,3-Diphenyl-3-acetoxy-1-propene was
prepared by acetylation of 1,3-diphenyl-2-propen-1-ol.
The isolated selenides 7a–7d, 8, 9 and 10 and N-to-
sylselenimides 3b–3d, 11a, 11b, 11d, 12 and 13 are new
compounds.
A white solid; 53% yield; 32% ee by Daicel Chiralcel
OD column with 25% 2-propanol–hexane; eluent,
AcOEt; 1H-NMR (400 MHz, CDCl3) l 2.34 (s, 3H,
Me), 4.18 (d, J=11.3 Hz, 1H, CHH), 4.54 (d, J=11.3
Hz, 1H, CHH), 6.95–7.74 (m, 14H, Ar); 13C-NMR
Table 6
Enantioselective Pd-catalyzed allylic alkylation a
(5)
Entry Ligand
Yield (%) b
ee (%) c Configuration
1
2
3
4
(4S,5S)-7a
3
5
4
72
82
71
–
(S)
(S)
(S)
–
(4S,5S)-8
(4S,5S)-9
(4S,5S)-11a
No reaction
a Acetate (0.6 mmol), CH2Cl2 (2.0 ml), BSA (three equivalents), CH2(CO2Me)2 (three equivalents), rt, 72 h.
b Isolated yield.
c The value was determined by HPLC using a suitable chiral column.

482
Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
4.2. Preparation of (4S,5S)-2-(4-tert-butyldimethyl-
silyloxymethyl-5-phenyloxazolin-2-yl)phenyl, phenyl
selenide (4S,5S)-(7a)
(100 MHz, CDCl3) l 21.3, 57.3, 126.0, 128.0, 128.9,
129.1, 129.2, 129.8, 130.3, 132.3, 141.1, 142.7.
4.1.2. Se-Benzyl-Se-(4-methoxyphenyl)-N-
(p-toluenesulfonyl)selenimide (3b)
sec-Butyllithium (23.0 ml of 1.06 M cyclohexane–
hexane solution, 24.4 mmol) was added to a stirred
A white solid; 37% yield; 20% ee by Daicel Chiralpak
AD column with 25% 2-propanol–hexane; eluent,
AcOEt; m.p. 144.0–145.0°C; IR (KBr) 1587, 1493,
solution
of
(4S,5S)-2-(4-tert-butyldimethylsilyl-
oxymethyl-5-phenyloxazolin-2-yl)benzene [25] (7.78 g,
21.2 mmol) and N,N,N%,N%-tetramethylethylenediamine
(TMEDA) (9.6 ml, 63.6 mmol) in THF (35 ml) at
−78°C. The resulting red solution was stirred at
−78°C for 15 min before the addition of a solution of
the corresponding diphenyl diselenide (6.61 g, 21.2
mmol) in THF (35 ml). The reaction mixture was
allowed to warm to room temperature and stirred for
24 h under nitrogen. The resulting yellow solution was
extracted with Et2O (50 ml×3) and the combined
organic phase was dried over anhydrous MgSO4,
filtered and concentrated under reduced pressure. Di-
aryl selenides (4S,5S)-7b–d were also prepared by this
method.
1255, 1126, 1082, 937, 828, 702, 662, 565 cm−1; H-
1
NMR (270 MHz, CDCl3) l 2.34 (s, 3H, Me), 3.83 (s,
3H, OMe), 4.14 (d, J=11.3 Hz, 1H, CHH), 4.53 (d,
J=11.3 Hz, 1H, CHH), 6.95–7.74 (m, 14H, Ar); 13C-
NMR (68 MHz, CDCl3) l 21.3, 55.6, 57.5, 115.3, 121.7,
126.0, 128.6, 128.9, 129.06, 129.13, 129.8, 130.4, 141.0,
142.7, 162.9; FAB LRMS m/z 448 (M+1)+; FAB
HRMS calc. for C21H21NO3SSe (M+1)+: 448.0486;
found: 448.0465. Anal. Calc. for C21H21NO3SSe: C,
56.50; H, 4.74; N, 3.14. Found: C, 55.18; H, 4.72; N,
3.16% [24].
Purification by silica gel column chlomatography af-
forded the title compound. A pale yellow oil; 42% yield;
eluent, hexane–AcOEt=40:1; [h]2D5 +21.0 (c 1.025,
CHCl3); IR (KBr) 3072, 2953, 2928, 1645 (CꢀN), 1470,
4.1.3. Se-Benzyl-Se-(1-naphthalenyl)-N-
(p-toluenesulfonyl)selenimide (3c)
A white solid; 23% yield; 29% ee by Daicel Chiralpak
AS column with 25% 2-propanol–hexane; eluent,
AcOEt; m.p. 43.0–44.0°C; IR (KBr) 1494, 1268, 1159,
1256, 1135, 1083, 1030, 836, 778, 742, 731, 696 cm−1
;
1H-NMR (270 MHz, CDCl3) l 0.14 (s, 6H, SiMe2),
0.94 (s, 9H, SiBut), 3.82 (dd, J=10.0, 7.6 Hz, 1H,
CHHOSi), 4.13 (dd, J=10.0, 4.0 Hz, 1H, CHHOSi),
4.45 (ddd, J=7.6, 6.1, 4.0 Hz, 1H, CHN), 5.61 (d,
J=6.1 Hz, 1H, CHO), 6.93–8.02 (m, 14H, Ar); 13C-
NMR (68 MHz, CDCl3) l −5.3, 18.2, 25.9, 65.3
(CH2O), 77.3 (CHN), 83.3 (CHO), 124.7, 125.3, 125.6,
127.9, 128.6, 128.9, 129.0, 129.7, 130.1, 131.0, 137.3,
138.6, 141.3, 163.2 (CꢀN); FAB LRMS m/z 524 (M+
1)+; FAB HRMS calc. for C28H33NO2SeSi (M+1)+:
524.1526; found: 524.1501. Anal. Calc. for
C28H33NO2SeSi: C, 64.35; H, 6.36; N, 2.68. Found: C,
63.57; H, 6.40; N, 2.61%.
1133, 1085, 938, 800, 768, 697, 568, 549 cm−1 1H-
;
NMR (400 MHz, CDCl3) l 2.31 (s, 3H, Me), 4.32 (d,
J=11.7 Hz, 1H, CHH), 4.50 (d, J=11.7 Hz, 1H,
CHH), 6.84–8.16 (m, 16H, Ar); 13C-NMR (100 MHz,
CDCl3) l 21.3, 56.5, 121.9, 125.9, 126.0, 126.9, 127.5,
127.8, 128.5, 128.9, 129.0, 129.1, 130.2, 131.0, 132.3,
133.6, 141.0, 142.7; FAB LRMS m/z 468 (M+1)+;
FAB HRMS calc. for C24H22NO2SSe (M+1)+:
468.0537; found: 468.0534. Anal. Calc. for
C24H22NO2SSe: C, 61.80; H, 4.54; N, 3.00. Found: C,
61.10; H, 4.47; N, 2.66% [24].
4.1.4. Se-Benzyl-Se-(2-naphthalenyl)-N-
(p-toluenesulfonyl)selenimide (3d)
4.2.1. (4S,5S)-2-(4-tert-butyldimethyl-
silyloxymethyl-5-phenyloxazolin-2-yl)phenyl,
2,4,6-trimethylphenyl selenide (4S,5S)-(7b)
A white solid; 64% yield; 36% ee by Daicel Chiralcel
OD column with 25% 2-propanol–hexane; eluent,
AcOEt; m.p. 156.0–157.0°C; IR (KBr) 1264, 1161,
A white solid; 45% yield; eluent, hexane–AcOEt=
40:1; m.p. 32.5–33.0°C; [h]2D5 +14.6 (c 1.29, CHCl3);
IR (KBr) 2952, 2926, 2854, 1645 (CꢀN), 1469, 1254,
1132, 1084, 946, 937, 814, 697 cm−1; H-NMR (270
1
1135, 1078, 1031, 1023, 835, 777, 730, 697 cm−1; H-
1
MHz, CDCl3) l 2.27 (s, 3H, Me), 4.26 (d, J=11.3
Hz, 1H, CHH), 4.58 (d, J=11.3 Hz, 1H, CHH),
6.94–7.92 (m, 16H, Ar); 13C-NMR (68 MHz, CDCl3) l
21.2, 57.2, 122.7, 125.9, 127.5, 128.0, 128.3, 128.4,
128.5, 128.8, 129.1, 129.18, 129.24, 129.9, 130.4, 132.8,
134.6, 141.0, 142.7; FAB LRMS m/z 468 (M+1)+;
FAB HRMS calc. for C24H22NO2SSe (M+1)+:
468.0537; found: 468.0535. Anal. Calc. for
C24H22NO2SSe: C, 61.80; H, 4.54; N, 3.00. Found: C,
60.06; H, 4.69; N, 3.33% [24].
NMR (400 MHz, CDCl3) l 0.14 (s, 3H, SiMeMe), 0.15
(s, 3H, SiMeMe), 0.93 (s, 9H, SiBut), 2.36 (s, 3H,
p-Me), 2.45 (s, 6H, o-Me), 3.89 (dd, J=10.3, 6.8 Hz,
1H, CHHOSi), 4.11 (dd, J=10.3, 3.9 Hz, 1H,
CHHOSi), 4.47 (ddd, J=6.8, 6.3, 3.9 Hz, 1H, CHN),
5.61 (d, J=6.3 Hz, 1H, CHO), 6.72–8.02 (m, 12H, Ar);
13C-NMR (100 MHz, CDCl3) l −5.3, 18.2, 21.1, 24.0,
25.9, 65.1 (CH2O), 77.5 (CHN), 82.7 (CHO), 124.3,
125.6, 127.4, 127.9, 128.3, 128.6, 128.8, 130.3, 131.0,
137.7, 139.2, 141.5, 144.2, 163.2 (CꢀN); FAB LRMS

Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
483
m/z 566 (M+1)+; FAB HRMS calc. for
C31H39NO2SeSi (M+1)+: 566.1996; found: 566.2001.
Anal. Calc. for C31H39NO2SeSi: C, 65.94; H, 6.96; N,
2.48. Found: C, 66.04; H, 6.98; N, 2.45%.
(TBAF) (2.0 ml of 1.0 M THF solution, 2.0 mmol) in
THF (15 ml) at room temperature. After extraction
with Et2O, the combined organic phase was dried over
anhydrous MgSO4, filtered and concentrated under re-
duced pressure.
4.2.2. (4S,5S)-2-(4-tert-butyldimethylsilyloxymethyl-
5-phenyloxazolin-2-yl)phenyl, 2,4,6-triisopropylphenyl
selenide (4S,5S)-(7c)
Purification by silica gel column chlomatography af-
forded the title compound. A white solid; 92% yield;
eluent, CH2Cl2; m.p. 33.5–34.5°C; [h]2D5 −4.7 (c 0.53,
CHCl3); IR (KBr) 3413 (OH), 1643 (CꢀN), 1468, 1436,
A pale yellow oil; 18% yield; eluent, hexane–
AcOEt=40:1; [h]2D5 +6.0 (c 1.33, CHCl3); IR (KBr)
2959, 2928, 2860, 1645 (CꢀN), 1464, 1255, 1135, 1078,
1333, 1275, 1257, 1136, 1035, 969, 742, 732, 695 cm−1
;
1H-NMR (300 MHz, CDCl3) l 2.22 (m, 1H, OH), 3.81
(m, 1H, CHHO), 4.10 (m, 1H, CHHO), 4.45 (m, 1H,
CHN), 5.52 (d, J=7.3 Hz, 1H, CHO), 6.94–7.94 (m,
1
1042, 1031, 836, 778, 731, 698 cm−1; H-NMR (400
MHz, CDCl3) l 0.13 (s, 3H, SiMeMe), 0.14 (s, 3H,
SiMeMe), 0.92 (s, 9H, SiBut), 1.15 (dd, J=6.8, 6.8 Hz,
12H, o-CHMe2), 1.32 (d, J=6.8 Hz, 6H, p-CHMe2),
2.96 (sep, J=6.8 Hz, 1H, p-CHMe2), 3.72 (sep, J=6.8
Hz, 2H, o-CHMe2), 3.92 (dd, J=10.3, 6.4 Hz, 1H,
CHHOSi), 4.08 (dd, J=10.3, 3.9 Hz, 1H, CHHOSi),
4.46 (ddd, J=6.4, 5.9, 3.9 Hz, 1H, CHN), 5.62 (d,
J=5.9 Hz, 1H, CHO), 6.73–8.00 (m, 12H, Ar); 13C-
NMR (100 MHz, CDCl3) l −5.3, 18.3, 23.9, 24.6,
25.9, 34.1, 34.3, 64.9 (CH2O), 77.2 (CHN), 82.6 (CHO),
122.1, 124.2, 125.3, 125.6, 127.4, 128.0, 128.6, 128.8,
130.3, 130.8, 139.4, 141.4, 150.6, 153.9, 163.4 (CꢀN);
FAB LRMS m/z 650 (M+1)+; FAB HRMS calc. for
C37H51NO2SeSi (M+1)+: 650.2936; found: 650.2932.
Anal. Calc. for C37H51NO2SeSi: C, 68.49; H, 7.92; N,
2.16. Found: C, 68.49; H, 8.03; N, 1.86%.
14H, Ar); 13C-NMR (75 MHz, CDCl3)
l 64.0
(CH2OH), 77.1 (CHN), 82.6 (CHO), 124.9, 125.4,
125.8, 128.4, 128.9, 129.0, 129.2, 129.7, 129.8, 130.0,
131.2, 137.1, 138.4, 140.4, 164.1 (CꢀN); FAB LRMS
m/z 410 (M+1)+; FAB HRMS calc. for C22H19NO2Se
(M+1)+: 410.0660; found: 410.0657. Anal. Calc. for
C22H19NO2Se: C, 64.71; H, 4.69; N, 3.43. Found: C,
64.53; H, 4.73; N, 3.32%.
4.2.5. Preparation of (4S,5S)-2-(4-methoxymethyl-5-
phenyloxazolin-2-yl)phenyl, phenyl selenide (4S,5S)-(9)
The selenide (4S,5S)-8 (0.65 g, 1.59 mmol) in THF (5
ml) was added dropwise at 0°C to a stirred solution of
abt. 60% sodium hydride (83.5 mg, 2.1 mmol; oil
removed by washing with 5 ml of dry hexane) in THF
(5 ml) under nitrogen. When the addition was com-
plete, the pale yellow solution was stirred at room
temperature for 30 min before the addition of methyl
iodide (0.13 ml, 2.0 mmol) at 0°C. The reaction mixture
was allowed to warm to room temperature and stirred
for an additional 4 h and slowly poured into 20 ml
ice-water, then extracted with Et2O. The combined
extract was dried over anhydrous MgSO4, filtered and
concentrated under reduced pressure.
4.2.3. (4S,5S)-2-(4-tert-butyldimethylsilyloxymethyl-5-
phenyloxazolin-2-yl)phenyl, 2-methoxyphenyl selenide
(4S,5S)-(7d)
A colorless oil; 5% yield; eluent, hexane–CH2Cl2=
1:1; [h]2D5 +23.2 (c 0.50, CHCl3); IR (KBr) 2953, 2928,
2855, 1645 (CꢀN), 1580, 1471, 1431, 1247, 1124, 1080,
1
1027, 974, 837, 777, 754, 732, 698 cm−1; H-NMR (300
MHz, CDCl3) l 0.16 (s, 3H, SiMeMe), 0.17 (s, 3H,
SiMeMe), 0.97 (s, 9H, SiBut), 3.83 (s, 3H, OMe), 3.84
(dd, J=9.5, 9.1 Hz, 1H, CHHOSi), 4.18 (dd, J=9.5,
4.1 Hz, 1H, CHHOSi), 4.48 (ddd, J=9.1, 6.1, 4.1 Hz,
1H, CHN), 5.63 (d, J=6.1 Hz, 1H, CHO), 6.93–8.04
(m, 13H, Ar); 13C-NMR (75 MHz, CDCl3) l −5.34,
18.2, 25.8, 55.8, 65.4 (CH2O), 77.2 (CHN), 83.3 (CHO),
111.1, 118.8, 121.6, 124.5, 125.4, 125.5, 127.8, 128.5,
128.8, 130.0, 130.7, 131.1, 137.6, 139.0, 141.3, 160.3,
163.2 (CꢀN); FAB LRMS m/z 554 (M+1)+; FAB
HRMS calc. for C29H35NO3SeSi (M+1)+: 554.1632;
found: 554.1633. Anal. Calc. for C29H35NO3SeSi: C,
63.03; H, 6.38; N, 2.53. Found: C, 62.91; H, 6.35; N,
2.37%.
Purification by silica gel column chlomatography af-
forded the title compound. A pale yellow oil; 87% yield;
eluent, hexane–AcOEt=2:1; [h]2D5 +37.5 (c 1.13,
CHCl3); IR (KBr) 1643 (CꢀN), 1469, 1435, 1331, 1135,
1
1089, 1030, 742, 731, 696 cm−1; H-NMR (400 MHz,
CDCl3) l 3.49 (s, 3H, OMe), 3.68 (dd, J=9.5, 8.5 Hz,
1H, CHHO), 3.88 (dd, J=9.5, 4.2 Hz, 1H, CHHO),
4.52 (ddd, J=8.5, 6.8, 4.2 Hz, 1H, CHN), 5.54 (d,
J=6.8 Hz, 1H, CHO), 6.94–7.99 (m, 14H, Ar); 13C-
NMR (100 MHz, CDCl3) l 59.4 (OMe), 74.6 (CH2O),
75.2 (CHN), 83.5 (CHO), 124.7, 125.2, 125.6, 128.1,
128.7, 128.9, 129.0, 129.7, 130.0, 131.1, 137.3, 138.6,
140.8, 163.4 (CꢀN); FAB LRMS m/z 424 (M+1)+;
FAB HRMS calc. for C23H21NO2Se (M+1)+:
424.0817; found: 424.0815. Anal. Calc. for
C23H21NO2Se: C, 65.40; H, 5.01; N, 3.32. Found: C,
65.41; H, 4.82; N, 3.17%.
4.2.4. Preparation of (4S,5S)-2-(4-hydroxymethyl-5-
phenyloxazolin-2-yl)phenyl, phenyl selenide (4S,5S)-(8)
Removal of the tert-butyldimethylsilyl protecting
group of (4S,5S)-7a (1.05 g, 2.0 mmol) was effected by
stirring with a solution of tetrabutylammonium fluoride

484
Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
4.2.6. (4S)-2-(4-Isopropyloxazolin-2-yl)phenyl, phenyl
selenide (4S)-(10)
CHHOSi), 4.29 (ddd, J=7.6, 6.4, 5.9 Hz, 1H, CHN),
5.49 (d, J=6.4 Hz, 1H, CHO), 6.90–8.97 (m, 18H, Ar);
a minor product l 0.12 (s, 3H, SiMeMe), 0.13 (s, 3H,
SiMeMe), 0.90 (s, 9H, SiBut), 2.35 (s, 3H, Me), 3.63
(dd, J=10.1, 4.4 Hz, 1H, CHHOSi), 3.80 (dd, J=10.1,
6.1 Hz, 1H, CHHOSi), 3.97 (ddd, J=6.2, 6.1, 4.4 Hz,
1H, CHN), 5.48 (d, J=6.2 Hz, 1H, CHO), 6.88–8.87
(m, 18H, Ar); 13C-NMR (75 MHz, CDCl3) a major
product l −5.6, 18.0, 21.2, 25.6, 64.1 (CH2O), 76.2
(CHN), 84.6 (CHO), 125.4, 125.9, 126.4, 128.3, 128.7,
128.8, 128.9, 129.4, 130.9, 131.8, 133.1, 135.3, 138.6,
139.6, 140.6, 143.5, 161.8 (CꢀN); a minor product l
−5.5, 18.1, 21.2, 25.7, 64.5 (CH2O), 75.9 (CHN), 84.2
(CHO), 125.3, 125.8, 126.3, 128.4, 128.6, 128.8, 129.1,
129.8, 130.9, 131.6, 133.0, 136.2, 139.1, 139.6, 140.5,
143.5, 161.9 (CꢀN); FAB LRMS m/z 693 (M+1)+;
FAB HRMS calc. for C35H40N2O4SSeSi (M+1)+:
693.1724; found: 693.1749. Anal. Calc. for
C35H40N2O4SSeSi: C, 60.77; H, 5.83; N, 4.05. Found:
C, 60.51; H, 5.82; N, 3.90%.
To
a
solution of (4S)-(4-isopropyloxazolin-2-
yl)benzene [17,26] (4.54 g, 24.0 mmol) and TMEDA
(10.8 ml, 71.6 mmol) in THF (50 ml) at −78°C was
added slowly sec-butyllithium (26.0 ml of 1.00 M cyclo-
hexane–hexane solution, 26.0 mmol). The resulting red
solution was stirred at −78°C for 3 h before the
addition of a solution of diphenyl diselenide (7.48 g,
24.0 mmol) in THF (50 ml). The reaction mixture was
allowed to warm to room temperature and stirred for
24 h under nitrogen. The resulting yellow solution was
extracted with Et2O (50 ml×3) and the combined
organic phase was dried over anhydrous MgSO4,
filtered and concentrated under reduced pressure.
Purification by silica gel column chromatography gave
the title compound. A pale yellow solid; 51% yield;
eluent, hexane–AcOEt=80:1; m.p. 44.0–45.0°C; [h]D25
−28.6 (c 2.09, CHCl3); IR (KBr) 2958, 2897, 1650
(CꢀN), 1467, 1436, 1357, 1250, 1135, 1082, 1047, 1029,
1
964, 742, 732, 695 cm−1; H-NMR (400 MHz, CDCl3)
l 1.02 (d, J=6.4 Hz, 3H, CHMeMe), 1.14 (d, J=6.8
Hz, 3H, CHMeMe), 1.86 (m, 1H, CHMe2), 4.13 (m,
1H, CHHO), 4.21 (m, 1H, CHN), 4.44 (m, 1H,
CHHO), 6.88–7.84 (m, 9H, Ar); 13C-NMR (100 MHz,
CDCl3) l 18.8, 19.1, 33.4, 70.3 (CHN), 73.5 (CHO),
124.6, 125.4, 128.8, 129.6, 129.7, 130.3, 130.7, 137.3,
138.5, 162.5 (CꢀN); FAB LRMS m/z 346 (M+1)+;
FAB HRMS calc. for C18H19NOSe (M+1)+:
346.0711; found: 346.0705. Anal. Calc. for
C18H19NOSe: C, 62.79; H, 5.56; N, 4.07. Found: C,
62.71; H, 5.50; N, 3.83%.
4.3.2. (4S,5S)-Se-[2-(4-tert-Butyldimethyl-
silyloxymethyl-5-phenyloxazolin-2-yl)phenyl]-Se-
2,4,6-trimethylphenyl-N-(p-toluenesulfonyl)selenimide,
(4S,5S)-(11b)
A colorless oil as a mixture of diastereomers; 64%
yield; 76% de; eluent, hexane–AcOEt=1:1; IR (KBr)
1
1656 (CꢀN), 1270 (SO2), 1129 (SO2) cm−1; H-NMR
(300 MHz, CDCl3) a major product l −0.08 (s, 3H,
SiMeMe), −0.01 (s, 3H, SiMeMe), 0.82 (s, 9H, SiBut),
2.11 (s, 6H, o-Me2), 2.23 (s, 3H, Me), 2.35 (s, 3H,
p-Me), 2.70 (dd, J=9.7, 9.5 Hz, 1H, CHHOSi), 3.38
(dd, J=9.7, 4.3 Hz, 1H, CHHOSi), 4.16 (ddd, J=9.5,
5.1, 4.3 Hz, 1H, CHN), 5.48 (d, J=5.1 Hz, 1H, CHO),
6.52–9.09 (m, 15H, Ar); a minor product l 0.04 (s, 3H,
SiMeMe), 0.07 (s, 3H, SiMeMe), 0.85 (s, 9H, SiBut),
2.11 (s, 6H, o-Me2), 2.21 (s, 3H, Me), 2.35 (s, 3H,
p-Me), 3.68–3.86 (m, 3H, CH2OSi and CHN), 5.34 (d,
J=5.7 Hz, 1H, CHO), 6.52–8.95 (m, 15H, Ar); 13C-
NMR (75 MHz, CDCl3) a mixture of diastereomers l
−5.7, −5.6, 20.6, 20.8, 20.9, 21.3, 25.6, 25.7, 63.9,
64.2, 75.6, 76.5, 84.0, 84.2, 125.0, 125.7, 126.0, 126.1,
126.4, 126.5, 128.2, 128.5, 128.6, 128.7, 128.8, 129.5,
129.8, 130.6, 131.0, 131.2, 131.5, 132.7, 132.8, 135.0,
135.4, 139.3, 139.7, 140.1, 140.4, 140.5, 141.0, 141.3,
143.7, 161.6, 161.8; FAB LRMS m/z 736 (M+1)+;
FAB HRMS calc. for C38H46N2O4SSeSi (M+1)+:
735.2194; found: 735.2182.
4.3. Typical procedure for diastereoselecti6e imidation
of diaryl selenide
To a solution of MS4A (ca. 80 mg) and Chloramine–
T trihydrate (67.6 mg, 0.24 mmol) in 1 ml of toluene,
the selenide (0.20 mmol) was added and the resulting
mixture was stirred under nitrogen at 25°C for 24 h.
Removal of the precipitate through Celite and evapora-
tion of the solvent gave a crude product. Purification by
silica gel column chromatography gave a pure selen-
1
imide. Diastereomeric excesses were determined by H-
NMR analysis.
4.3.1. (4S,5S)-Se-[2-(4-tert-Butyldimethyl-
silyloxymethyl-5-phenyloxazolin-2-yl)phenyl]-Se-
phenyl-N-(p-toluenesulfonyl)selenimide, (4S,5S)-(11a)
A white solid as a mixture of diastereomers; 92%
yield; 67% de; eluent, hexane–AcOEt=1:1; m.p. 58–
59°C; IR (KBr) 1650 (CꢀN), 1261 (SO2), 1131 (SO2)
4.3.3. (4S,5S)-Se-[2-(4-tert-Butyldimethyl-
silyloxymethyl-5-phenyloxazolin-2-yl)phenyl]-Se-2-
methoxyphenyl-N-(p-toluenesulfonyl)selenimide,
(4S,5S)-(11d)
A colorless oil as a mixture of diastereomers; 75%
yield; 30% de; eluent, hexane–AcOEt=1:3; IR (KBr)
1
cm−1; H-NMR (300 MHz, CDCl3) a major product l
−0.03 (s, 3H, SiMeMe), 0.02 (s, 3H, SiMeMe), 0.84 (s,
9H, SiBut), 2.36 (s, 3H, Me), 3.16 (dd, J=10.3, 7.6 Hz,
1H, CHHOSi), 4.10 (dd, J=10.3, 5.9 Hz, 1H,

Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
485
1651 (CꢀN), 1338 (SO2), 1275, 1128 (SO2), 1084, 937
1H-NMR (270 MHz, CDCl3) a major product l 0.48 (d,
J=6.9 Hz, 3H, CHMeMe), 0.63 (d, J=6.9 Hz, 3H,
CHMeMe), 1.59 (m, 1H, CHMe2), 2.35 (s, 3H, Me),
3.85–4.45 (m, 3H, CH2O and CHN), 7.13–8.67 (m,
13H, Ar); a minor product l 0.98 (d, J=6.6 Hz, 3H,
CHMeMe), 1.08 (d, J=6.6 Hz, 3H, CHMeMe), 1.80
(m, 1H, CHMe2), 2.33 (s, 3H, Me), 3.90–4.45 (m, 3H,
CH2O and CHN), 7.11–8.80 (m, 13H, Ar); 13C-NMR
(68 MHz, CDCl3) a major product l 17.3 (CHMeMe),
18.4 (CHMeMe), 21.3, 31.9 (CHMe2), 70.5 (CHN), 72.6
(CHO), 125.9, 127.0, 128.2, 128.9, 129.2, 129.5, 130.9,
131.7, 132.9, 134.9, 138.5, 140.6, 143.6, 161.5 (CꢀN); a
minor product l 19.0 (CHMeMe), 19.1 (CHMeMe),
21.3, 33.1 (CHMe2), 71.5 (CHN), 72.7 (CHO), 126.2,
128.3, 128.4, 128.8, 128.9, 129.4, 131.5, 136.2, 138.7,
140.5, 161.4 (CꢀN); FAB LRMS m/z 515 (M+1)+;
FAB HRMS calc. for C25H26N2O3SSe (M+1)+:
515.0909; found: 515.0920. Anal. Calc. for
C25H26N2O3SSe: C, 58.47; H, 5.10; N, 5.46. Found: C,
58.37; H, 4.95; N, 5.39%.
1
cm−1; H-NMR (300 MHz, CDCl3) a major product l
−0.09 (s, 3H, SiMeMe), −0.05 (s, 3H, SiMeMe), 0.81
(s, 9H, SiBut), 2.37 (s, 3H, Me), 2.66 (dd, J=9.7, 9.5
Hz, 1H, CHHO), 3.37 (dd, J=9.7, 4.2 Hz, 1H,
CHHO), 3.62 (s, 3H, OMe), 4.18 (ddd, J=9.5, 6.1, 4.2
Hz, 1H, CHN), 5.43 (d, J=6.1 Hz, 1H, CHO), 6.63–
8.94 (m, 17H, Ar); a minor product l 0.102 (s, 3H,
SiMeMe), 0.104 (s, 3H, SiMeMe), 0.88 (s, 9H, SiBut),
2.36 (s, 3H, Me), 3.69 (s, 3H, OMe), 3.70–3.93 (m, 3H,
CH2O and CHN), 5.45 (d, J=6.4 Hz, 1H, CHO),
6.63–8.11 (m, 17H, Ar); 13C-NMR (75 MHz, CDCl3) a
mixture of diastereomers l −5.6, −5.5, −5.4, 18.0,
18.1, 21.2, 25.66, 25.70, 55.86, 55.92, 63.9, 64.3, 75.8,
75.9, 84.6, 84.9, 111.2, 122.0, 122.1, 125.3, 125.4, 126.06,
126.13, 126.4, 126.7, 127.5, 127.8, 127.9, 128.25, 128.31,
128.58, 128.63, 128.7, 128.8, 129.7, 129.8, 130.4, 130.7,
131.5, 131.7, 132.5, 132.7, 132.8, 133.1, 133.8, 134.9,
139.9, 140.1, 140.2, 143.9, 156.7, 156.8, 161.7, 162.0;
FAB LRMS m/z 723 (M+1)+; FAB HRMS calc. for
C36H42N2O5SSeSi (M+1)+: 723.1830; found: 723.1801.
4.3.6. (4S,SSe)-Se-[2-(4-Isopropyloxazolin-2-yl)phenyl]-
Se-phenyl-N-(p-toluenesulfonyl)selenimide, (4S,SSe)-(13)
Purification by recrystallization from n-hexane–
CH2Cl2 afforded the title compound. A colorless crystal;
99% de; m.p. 185.0–185.5°C; [h]2D5 −161.8 (c 0.22,
CHCl3); IR (KBr) 1650 (CꢀN), 1269 (SO2), 1128 (SO2),
4.3.4. (4S,5S)-Se-[2-(4-Methoxymethyl-5-
phenyloxazolin-2-yl)phenyl]-Se-phenyl-N-
(p-toluenesulfonyl)selenimide, (4S,5S)-(12)
A white solid as a mixture of diastereomers; 92%
yield; 55% de; eluent, hexane–AcOEt=1:3; m.p.
100.0–102.0°C; IR (KBr) 1651 (CꢀN), 1341 (SO2), 1269,
1129 (SO2), 1082, 933 cm−1 1H-NMR (300 MHz,
;
1
1082 cm−1; H-NMR (270 MHz, CDCl3) l 0.49 (d,
CDCl3) a major product l 2.34 (s, 3H, Me), 3.19 (s, 3H,
OMe), 3.24 (dd, J=9.7, 5.3 Hz, 1H, CHHO), 3.39 (dd,
J=9.7, 4.4 Hz, 1H, CHHO), 4.33 (ddd, J=7.5, 5.3, 4.4
Hz, 1H, CHN), 5.44 (d, J=7.5 Hz, 1H, CHO), 7.13–
8.80 (m, 18H, Ar); a minor product l 2.35 (s, 3H, Me),
3.46 (s, 3H, OMe), 3.61 (dd, J=9.7, 6.1 Hz, 1H,
CHHO), 3.72 (dd, J=9.7, 4.2 Hz, 1H, CHHO), 4.14
(ddd, J=6.1, 4.6, 4.2 Hz, 1H, CHN), 5.47 (d, J=4.6
Hz, 1H, CHO), 6.90–8.83 (m, 18H, Ar); 13C-NMR (75
MHz, CDCl3) a major product l 21.3, 59.0 (CH2O),
72.9 (OMe), 74.5 (CHN), 84.2 (CHO), 125.7, 126.0,
126.3, 128.5, 128.8, 128.95, 128.96, 129.01, 129.4, 130.0,
130.9, 131.7, 133.2, 135.9, 138.6, 139.2, 140.6, 143.6,
161.9 (CꢀN); a minor product l 21.3, 59.5 (CH2O), 73.8
(OMe), 74.1 (CHN), 84.5 (CHO), 125.4, 125.9, 126.2,
128.5, 128.7, 128.9, 129.0, 129.5, 129.9, 130.9, 131.6,
133.1, 136.6, 139.2, 139.5, 140.6, 143.5, 162.1 (CꢀN);
FAB LRMS m/z 593 (M+1)+; FAB HRMS calc. for
C30H28N2O4SSe (M+1)+: 593.1015; found: 593.1022.
Anal. Calc. for C30H28N2O4SSe: C, 60.91; H, 4.77; N,
4.74. Found: C, 60.10; H, 4.75; N, 4.63%.
J=6.9 Hz, 3H, CHMeMe), 0.64 (d, J=6.9 Hz, 3H,
CHMeMe), 1.60 (m, 1H, CHMe2), 2.35 (s, 3H, Me),
4.06–4.20 (m, 2H, CHHO and CHN), 4.43 (dd, J=8.5,
7.1 Hz, 1H, CHHO), 7.13–8.68 (m, 13H, Ar); 13C-
NMR (68 MHz, CDCl3) l 17.3 (CHMeMe), 18.4
(CHMeMe), 21.3, 31.8 (CHMe2), 70.5 (CHN), 72.6
(CHO), 125.9, 127.0, 128.1, 128.9, 129.2, 129.5, 130.8,
131.7, 132.8, 134.8, 138.4, 140.6, 143.6, 161.5 (CꢀN);
FAB LRMS m/z 515 (M+1)+; FAB HRMS calc. for
C25H26N2O3SSe (M+1)+: 515.0909; found: 515.0908.
Anal. Calc. for C25H26N2O3SSe: C, 58.47; H, 5.10; N,
5.46. Found: C, 58.40; H, 5.01; N, 5.43%.
4.4. X-ray structural analysis of (4S,SSe)-13
The measurement was carried out on a Bruker
SMART CCD detector system using graphite-
,
monochromated Mo–Ka (u=0.71073 A) radiation
from a sealed-tube X-ray source at 299 K. The SMART
software package [27] was used for data collection as
well as frame integration. Structure solution and refine-
ment were carried out using the SHELXTL software
package [28]. The structure was solved by direct meth-
ods. Full-matrix least-squares refinement was carried
out against F2. The non-hydrogen atoms were refined
anisotropically. All hydrogen atoms were geometrically
4.3.5. (4S)-Se-[2-(4-Isopropyloxazolin-2-yl)phenyl]-Se-
phenyl-N-(p-toluenesulfonyl)selenimide, (4S)-(13)
A pale yellow solid as a mixture of diastereomers;
92% yield; 55% de; eluent, hexane–AcOEt=1:1; IR
(KBr) 1650 (CꢀN), 1269 (SO2), 1128 (SO2), 1082 cm−1
;

486
Y. Miyake et al. / Journal of Organometallic Chemistry 611 (2000) 475–487
fixed and allowed to ride on the attached atoms. The
crystallographic data are listed in Table 8.
ligand (4S,5S)-7a (3.3 mg, 0.006 mmol) under a nitro-
gen atmosphere. After 30 min, acetophenone (0.12 ml,
1.00 mmol) was added. The solution was then allowed
to be stirred for 1 h. After addition of diphenylsilane
(0.25 ml, 1.35 mmol), the solution was stirred for 20 h.
To quench the reaction, MeOH (3 ml) and 1 N HCl (1
ml) were added. The resulting solution was extracted
with Et2O (10 ml×3) and the combined organic phases
were dried over anhydrous MgSO4, filtered and concen-
trated under reduced pressure. Purification by distilla-
tion afforded the pure sec-phenethyl alcohol. The
optical purity was determined by GLC analysis using
TCI Chiraldex G-TA column.
4.5. Typical procedure of enantioselecti6e allylic
alkylation
To a stirring solution of [Pd(h3-C3H5)Cl]2 (2.9 mg,
0.008 mmol) in CH2Cl2 (1 ml) was added the chiral
selenide ligand (4S,5S)-7a (17.2 mg, 0.033 mmol) under
a nitrogen atmosphere. After 15 min, racemic 1,3-
diphenyl-3-acetoxy-1-propene (150 mg, 0.60 mmol) was
added. The solution was then allowed to be stirred for
30 min. N,O-Bis(trimethylsilyl)acetamide (0.44 ml, 1.8
mmol), dimethyl malonate (0.21 ml, 1.8 mmol) and
potassium acetate (3.0 mg, 0.03 mmol) were added in
this order. After the solvent was evaporated under
reduced pressure, silica gel column chromatography of
the residue yielded the pure dimethyl (1,3-diphenyl-2-
propen-1-yl)propanedioate. The optical purity was de-
termined by HPLC using Daicel Chiralpak AD column.
5. Supplementary material
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 141693 for (4S,SSe)-13. Copies
of this information may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cam-
bridge, CB2, 1EZ, UK (Fax: +44-1223-336033; e-mail:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.
cam.ac.uk).
4.6. Typical procedure of enantioselecti6e
hydrosilylation
To a stirring solution of [Rh(cod)Cl]2 (1.3 mg, 0.003
mmol) in THF (3 ml) was added the chiral selenide
Table 8
Crystal data and structure refinement for (4S,SSe)-13
Acknowledgements
Empirical formula
Formula weight
Temperature (K)
C25H26N2O3SSe
513.50
299
We thank Mr Kenji Yoza of Bruker Japan Co. Ltd.
for the X-ray crystallographic analysis and Dr
Masahiro Ebitani of Gifu University for helpful discus-
sion on X-ray analysis. We also thank Mr Yasuaki
Hisamoto for low-resolution mass spectra (LRMS) and
high-resolution mass spectra (HRMS) analyses. This
work was supported by a Grant-in-Aid for Scientific
Research on Priority Areas (A), The Chemistry of
Inter-Element Linkage (No. 11120226) from the Min-
istry of Education, Science, Sports and Culture, Japan.
,
Wavelength (A)
Crystal system
Space group
0.71073
Orthorhombic
P2(1)2(1)2(1)
Unit cell dimensions
,
a (A)
9.5674(5)
9.8667(6)
26.1167(14)
90
90
90
2465.4(2)
4
1.383
1.636
0.05×0.10×0.19
1.56–24.70
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
Volume (A )
Z
Density (calculated) (Mg m−3
)
)
Absorption coefficient (mm−1
Crystal size (mm)
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