Asymmetric 1,4-addition of aryltrialkoxysilanes to α,β-unsaturated esters and amides catalyzed by a chiral rhodium complex

Article abstract of DOI:10.1016/j.tetasy.2005.12.032

A highly enantioselective 1,4-addition of aryltrialkoxysilanes to α,β-unsaturated esters and amides was successfully catalyzed by a chiral rhodium complex generated from [Rh(cod)(MeCN)₂]BF₄ and (S)-BINAP.

Full text of DOI:10.1016/j.tetasy.2005.12.032

Tetrahedron: Asymmetry 17 (2006) 598–602
Asymmetric 1,4-addition of aryltrialkoxysilanes to
a,b-unsaturated esters and amides catalyzed by
a chiral rhodium complex
Shuichi Oi,* Akio Taira, Yoshio Honma, Takashi Sato and Yoshio Inoue*
Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
Received 17 November 2005; accepted 29 December 2005
Available online 20 February 2006
Abstract—A highly enantioselective 1,4-addition of aryltrialkoxysilanes to a,b-unsaturated esters and amides was successfully cata-
lyzed by a chiral rhodium complex generated from [Rh(cod)(MeCN)2]BF4 and (S)-BINAP.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
reaction of the corresponding organic halides with
disilanes16 or hydrosilanes.17 With regard to the
rhodium-catalyzed reaction of organosilicon reagents,
we have reported the addition of phenylmethyldifluoros-
ilane to aldehydes.18 The addition of diaryldichlorosil-
anes to unsaturated carbonyl compounds,19 and the
addition of arylmethylsilanediols to unsaturated car-
bonyl compounds and aldehydes20 have been also
reported. We21 and Murata and Masuda22 reported
the 1,4-addition of organotrialkoxysilanes to a,b-unsat-
urated ketones catalyzed by rhodium complexes, which
was then expanded to an asymmetric version by the
use of rhodium–BINAP complexes as asymmetric catal-
ysts.23,24 The 1,4-addition of organosilicon compounds
has also been found to be catalyzed by palladium com-
plexes.25 Herein, we report that the rhodium–BINAP
complex-catalyzed asymmetric 1,4-addition of aryltri-
alkoxysilanes can be successfully applied to a,b-unsatu-
rated esters and amides.
Transition metal-catalyzed transformations using organo-
metallic reagents are of great importance in modern
organic chemistry.1 In particular, asymmetric carbon–
carbon bond forming processes are being emphasized
in advanced materials and pharmaceuticals. The
asymmetric 1,4-conjugate addition of organometallic
reagents to a,b-unsaturated carbonyl compounds is
widely used for carbon–carbon bond formation, with a
new stereogenic center being introduced at the b-posi-
tion of the saturated carbonyl compounds formed.2
Rhodium-catalyzed asymmetric 1,4-addition of organo-
boronic acids3 was first reported by Hayashi and
Miyaura4 and has been widely studied.5,6 Other
organometallic reagents, such as organo-titanium,7 -zir-
conium,8,9 -zinc,10 and -tin11,12 have also been applied
successfully for the rhodium-catalyzed 1,4-addition.
Organosilicon reagents are playing a growing role in
organic synthesis due to their low cost, low toxicity, ease
of handling, tolerance to a variety of functional groups,
and simplicity of by-product removal.13 A synthetic
advantage is that the organosilicon reagents are readily
prepared in one step by a variety of methods. For
example, b-substituted E- and Z-vinylsilanes14 and a-
substituted ones15 can be prepared by regio- and stereo-
selective hydrosilylation of alkynes, and acyl-, alkyl-,
vinyl-, and arylsilanes can be prepared by cross-coupling
2. Results and discussion
2.1. Asymmetric addition to a,b-unsaturated esters
The reactions of aryltrialkoxysilanes with a,b-unsatu-
rated esters were performed in the presence of a cationic
rhodium complex, [Rh(cod)(MeCN)2]BF4 (4 mol %),
and (S)-BINAP (6 mol %) in 1,4-dioxane/water (10:1)
at 90 °C for 20 h. Results are summarized in Table 1.
In the reactions of phenyltrimethoxysilane 2a with linear
a,b-unsaturated esters, enantioselectivity and reactivity
*
Corresponding authors. Tel./fax: +81 22 795 5876; e-mail: oishu@
aporg.che.tohoku.ac.jp
0957-4166/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2005.12.032

S. Oi et al. / Tetrahedron: Asymmetry 17 (2006) 598–602
599
Table 1. Asymmetric 1,4-addition of aryltrialkoxysilanes to a,b-
2.2. Asymmetric addition to a,b-unsaturated amides
unsaturated estersa
The asymmetric 1,4-addition of aryltrialkoxysilane was
then applied to a,b-unsaturated amides. Results are
summarized in Table 2. The reactivity of the a,b-unsatu-
rated amides were slightly lower than that of esters.
Thus the yields were lower than those of the esters
derived from the corresponding carboxylic acids. The
reaction of phenyltrimethoxysilane 2a with (E)-2-
butenamide 4a gave the corresponding product 5aa in
75% yield and 81% ee, while the reaction of 2a with
(E)-2-hexenamide 4b gave the product 5ab in 59% yield
with a higher enantioselectivity of 91% ee (entries 1 and
2). The reaction of 2a with 4c having an isopropyl group
at the olefin terminal (R1 = Pri) did not proceed with the
steric hindrance of the isopropyl group (entry 3). Sub-
stituents on the nitrogen atom of an amide moiety
affected the enantioselectivity. The N,N-dimethyl amide
of crotonic acid 4d showed a lower enantioselectivity of
72% ee than that of 4a (81% ee, entry 1), while N-benzyl
amide 4e showed a higher enantioselectivity of 92% ee
(entries 4 and 5). The reaction of 4e with 4-substituted
phenyltriethoxysilane (2b and 2c) proceeded well, afford-
ing the corresponding products 5eb and 5ec in moderate
yield (30% and 54%, respectively) with high enantio-
selectivity (90% ee and 92% ee, respectively) (entries 6
and 7).
O
Ar
O
cat. Rh/(S)-BINAP
dioxane/H2O
Ar Si(OR)3
+
R1
OR2
R1
OR2
1
2
3
1a: R1=Me, R2=Me
1b: R1=Me, R2=Et
1c: R1=Me, R2=Pri
1d: R1=Prn, R2=Me
1e: R1=Prn, R2=Pri
1f: R1=Pri, R2=Me
1g: R1=Pri, R2=Pri
2a: Ar=Ph, R=Me
2b: Ar=4-MeO-C6H4, R=Et
2c: Ar=4-Cl-C6H4, R=Et
1h:
O
O
Entry
1
2
Product
Yield (%)b
ee (%)c
1
2
3
4
5
6
7
8
9
1a
1b
1c
1d
1e
1f
2a
2a
2a
2a
2a
2a
2a
2a
2b
2c
3aa
3ba
3ca
3da
3ea
3fa
3ga
3ha
3cb
3cc
93
70
76
70
76
36
28
64
84
80
84 (R)
89 (R)
93
85
93
94 (S)
97 (S)
99 (S)
88
1g
1h
1c
1c
10
93
a Common reaction conditions:
1
(1.0 mmol),
2
(2.0 mmol),
[Rh(cod)(MeCN)2]BF4 (0.04 mmol), (S)-BINAP (0.06 mmol),
2.2 mL of dioxane/H2O (10:1), 90 °C, 20 h, N2 atmosphere.
b Isolated yield.
c Determined by HPLC using chiral stationary phase column: Daicel
Chiralcel OD-H (3aa, 3ba, 3ca, 3da, 3ea, 3fa, 3ga, 3cb) (hexane/2-
propanol = 100:1), OG (3ha) (hexane/2-propanol = 90:10), OB-H
(3cc) (hexane). Absolute configuration is shown in parenthesis.
Table 2. Asymmetric 1,4-addition of aryltrialkoxysilanes to a,b-
unsaturated amidesa
O
Ar
O
R3
R3
cat. Rh/(S)-BINAP
dioxane/H2O
R1
N
R2
R1
N
R2
Ar Si(OR)3
+
4
2
5
4a: R1=Me, R2=R3=H
4b: R1=Prn, R2=R3=H
4c: R1=Pri, R2=R3=H
4d: R1=R2=R3=Me
2a: Ar=Ph, R=Me
2b: Ar=4-MeO-C6H4, R=Et
2c: Ar=4-Cl-C6H4, R=Et
were affected by the bulkiness of both the substituents
on the olefin terminal and the alkoxycarbonyl moiety.
Generally, the bulkiness of these substituents heightened
the enantioselectivity but lowered the yield. For exam-
ple, the reaction of methyl (E)-4-methyl-2-pentenoate
1f, which has an isopropyl group at the olefin terminal
(R1 = Pri) showed a higher enantioselectivity (94% ee)
than that of methyl crotonate 1a (84% ee) having a
methyl group at the olefin terminal (R1 = Me), while
the yield was lower in the case of 1f (36%) than 1a
(93%) (entries 1 and 6). Similarly, the reaction of isoprop-
yl crotonate 1c (R2 = Pri) showed a higher enantio-
selectivity (93% ee) than that of methyl crotonate 1a
(R2 = Me, 84% ee), while the yield was lower in the case
of 1c (76%) than 1a (93%) (entries 1 and 3). Therefore,
the highest enantioselectivity and the lowest yield in
the linear substrate was observed in the reaction of 1g
(R1 = R2 = Pri) (97% ee and 28% yield) (entry 7). On
the other hand, the reaction of cyclic substrate 1h
showed excellent enantioselectivity, affording product
3ha in 64% yield with 99% ee (entry 8). The reaction
of 1c with 4-substituted phenyltriethoxysilane 2b and
2c also proceeded well, affording the corresponding
products 3cb and 3cc in good yield (84% and 80%,
respectively) with high enantioselectivity (88% ee and
93% ee, respectively) (entries 9 and 10).
4e: R1=Me, R2=H, R3=CH2Ph
Entry
4
2
Product
Yield (%)b
ee (%)c
1
2
3
4
5
6
7
4a
4b
4c
4d
4e
4e
4e
2a
2a
2a
2a
2a
2b
2c
5aa
5ba
5ca
5da
5ea
5eb
5ec
75
59
Trace
61
70
81 (R)
91
72 (R)
92
90
30
54
92
a Common reaction conditions:
4
(1.0 mmol),
2
(2.0 mmol),
[Rh(cod)(MeCN)2]BF4 (0.04 mmol), (S)-BINAP (0.06 mmol),
2.2 mL of dioxane/H2O (10:1), 90 °C, 20 h, N2 atmosphere.
b Isolated yield.
c Determined by HPLC using chiral stationary phase column: Daicel
Chiralpak AD (hexane/2-propanol = 95:5). Absolute configuration
is shown in parenthesis.
3. Conclusion
Enantioselective 1,4-addition of aryltrialkoxysilanes to
a,b-unsaturated esters and amides, catalyzed by a chiral

600
S. Oi et al. / Tetrahedron: Asymmetry 17 (2006) 598–602
24
rhodium complex generated from [Rh(cod)(MeCN)2]-
BF4 and (S)-BINAP is described. Aryl groups can be
introduced easily and enantioselectively at the b-posi-
tion of a variety of esters and amides. Enantioselectivity
and chemical yield were affected by the bulkiness of the
substituents on olefin terminal and also by the ester or
amide moiety.
60.2, 43.0, 36.5, 21.8, 14.1. ½aꢀD ¼ ꢁ29 (c 1.05, Et2O)
22
89% ee (R) (lit.29 ½aꢀD ¼ þ21:4 (c 1.538, Et2O) 95% ee (S)).
4.3.3. 3-Phenylbutanoic acid isopropyl ester 3ca.30 1H
NMR (400 MHz, CDCl3) d 7.30–7.16 (m, 5H), 4.94
(sep, J = 6.4 Hz, 1H), 3.26 (sext, J = 7.2 Hz, 1H),
2.60–2.48 (m, 2H), 1.29 (d, J = 6.8 Hz, 3H), 1.16 (d,
J = 6.4 Hz, 3H), 1.11 (d, J = 6.4 Hz, 3H). 13C NMR
(100 MHz, CDCl3) d 171.9, 145.7, 128.4, 126.8, 126.3,
24
4. Experimental
4.1. General
67.5, 43.3, 36.6, 21.8, 21.7, 21.6. ½aꢀD ¼ ꢁ25 (c 1.03,
CHCl3) 93% ee.
4.3.4. 3-Phenylhexanoic acid methyl ester 3da.6a 1H
NMR (400 MHz, CDCl3) d 7.30–7.17 (m, 5H), 3.58 (s,
3H), 3.10 (quint, J = 6.8 Hz, 1H), 2.66–2.54 (m, 2H),
1.63–1.57 (m, 2H), 1.21–1.13 (m, 2H), 0.85 (t,
J = 7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3) d
Infrared (IR) spectra were recorded on JASCO FT/
IR-350 Fourier transform infrared spectrophotometer.
NMR spectra were recorded on Bruker DPX-400 or
DRX-500 spectrometer using TMS as an internal stan-
dard. All reactions were carried out in Schlenk tubes
under N2. Flash chromatographies were performed
using spherical silica gel (40–100 lm, Kanto Chemical).
Elemental analyses were performed by the Microanalyti-
cal Laboratory of the Institute for Chemical Reaction
Science, Tohoku University.
172.9, 144.1, 128.4, 127.4, 126.4, 51.4, 41.9, 41.6, 38.4,
21
20.4, 13.9. ½aꢀD ¼ ꢁ15 (c 0.97, CHCl3) 85% ee {lit.6a
20
½aꢀD ¼ ꢁ20 (c 0.90, CHCl3) > 99% ee}.
4.3.5. 3-Phenylhexanoic acid isopropyl ester 3ea.6a 1H
NMR (500 MHz, CDCl3) d 7.29–7.16 (m, 5H), 4.89
(sept, J = 6.5 Hz, 1H), 3.12–3.06 (m, 1H), 2.58 (dd,
J = 15, 7 Hz, 1H), 2.51 (dd, J = 15, 7 Hz, 1H), 1.63–
1.57 (m, 2H), 1.21–1.16 (m, 2H), 1.12 (d, J = 6 Hz,
3H), 1.05 (d, J = 6 Hz, 3H), 0.85 (t, J = 7.5 Hz, 3H).
13C NMR (125 MHz, CDCl3) d 172.0, 144.1, 128.3,
4.2. Materials
1,4-Dioxane was distilled and stored under N2. The cat-
ionic rhodium complex, [Rh(cod)(MeCN)2]BF4, was
prepared as described in the literature.26 Phenyltri-
methoxysilane 2a was purchased from TCI Co., Ltd.
p-Chlorophenyltriethoxysilane 2b and p-methoxy-
phenyltriethoxysilane 2c were prepared by cross-coup-
ling reaction of the corresponding aryl bromide with
triethoxysilane as described in the literature.17d
127.5, 126.3, 67.4, 42.1, 42.1, 38.5, 21.7, 21.6, 20.4,
22
13.9. ½aꢀD ¼ ꢁ17 (c 0.98, CHCl3) 93% ee {lit.6a
24
½aꢀD ¼ ꢁ18 (c 1.09, CHCl3) 95% ee}.
4.3.6. 4-Methyl-3-phenylpentanoic acid methyl ester
3fa.31 1H NMR (400 MHz, CDCl3) d 7.29–7.13 (m,
5H), 3.51 (s, 3H), 2.89 (ddd, J = 10, 7.6, 5.6 Hz, 1H),
2.79 (dd, J = 15, 5.6 Hz, 1H), 2.6 (dd, J = 15, 8.4 Hz,
1H), 1.86 (oct, J = 7.6 Hz, 1H), 0.94 (d, J = 6.8 Hz,
3H), 0.75 (d, J = 6.4 Hz, 3H). 13C NMR (100 MHz,
4.3. General procedure for rhodium-catalyzed asymmetric
1,4-addition
To a mixture of [Rh(cod)(MeCN)2]BF4 (15.2 mg,
0.04 mmol) and (S)-BINAP (37.4 mg, 0.06 mmol) in
1,4-dioxane (2 mL) was added a,b-unsaturated carbonyl
compound 1 or 4 (1.0 mmol), aryltrialkoxysilane 2
(2.0 mmol), and then water (0.2 mL). The mixture was
stirred at 90 °C for 20 h. Hexane (100–150 mL) was
added to the reaction mixture and the resulting precipi-
tate removed by filtration. The solvent was removed in
vacuo and the residue purified by flash chromatography
(hexane/AcOEt) to give the 1,4-addition product 3 or 5.
CDCl3) d 173.2, 142.8, 128.1, 128.0, 126.3, 51.4, 48.8,
22
38.3, 33.0, 20.6, 20.3. ½aꢀD ¼ ꢁ26 (c 0.97, CHCl3)
25
94% ee (S) {lit.32 ½aꢀD ¼ þ33:5 (neat) (R)}.
4.3.7. 4-Methyl-3-phenylpentanoic acid isopropyl ester
3ga.6a 1H NMR (500 MHz, CDCl3) d 7.27–7.13 (m,
5H), 4.82 (sept, 6 Hz, 1H), 2.85 (ddd, J = 10.5, 7.5,
5.5 Hz, 1H), 2.74 (dd, J = 14.5, 5.5 Hz, 1H), 2.55 (dd,
J = 14.5, 10 Hz, 1H), 1.84 (oct, J = 7 Hz, 1H), 1.06
(d, J = 6.5 Hz, 3H), 0.97 (d, J = 6.2 Hz, 3H), 0.96 (d,
J = 6.8 Hz, 3H), 0.76 (d, J = 6.7 Hz, 3H). 13C NMR
4.3.1. 3-Phenylbutanoic acid methyl ester 3aa.27 1H
NMR (500 MHz, CDCl3) d 7.32–7.16 (m, 5H), 3.61 (s,
3H), 3.28 (sext, J = 7.5 Hz, 1H), 2.58 (m, 2H), 1.29 (d,
J = 7.2 Hz, 3H). 13C NMR (125 MHz, CDCl3) d
(125 MHz, CDCl3) d 172.3, 142.8, 128.3, 128.0, 126.2,
22
67.3, 49.1, 38.9, 33.3, 21.6, 21.5, 20.6, 20.4. ½aꢀD ¼ ꢁ23
20
(c 1.02, CHCl3) 97% ee (S) {lit.6a ½aꢀD ¼ ꢁ23 (c 1.19,
CHCl3) 98% ee(S)}.
172.8, 145.7, 130.8, 128.5, 128.2, 126.7, 126.4, 51.4,
26
42.7, 36.4, 21.7. ½aꢀD ¼ ꢁ26 (c 1.00, CHCl3) 84% ee
4.3.8. 4-(Phenyl)tetrahydro-2H-pyran-2-one 3ha.6a 1H
NMR (500 MHz, CDCl3) d 7.37–7.33 (m, 2H), 7.28–
7.25 (m, 1H), 7.21–7.17 (m, 2H), 4.48 (ddd, J = 11.4,
4.7, 3.9 Hz, 1H), 4.39–4.33 (m, 1H), 3.24–3.18 (m, 1H),
2.89 (ddd, J = 17.6, 6, 1.7 Hz, 1H), 2.61 (dd, J = 17.6,
10.6 Hz, 1H), 2.18–2.12 (m, 1H), 2.05–1.97 (m, 1H). 13C
24
(R) {lit.28 ½aꢀD ¼ ꢁ25:3 (c 1.07, CHCl3) 95% ee (R)}.
4.3.2. 3-Phenylbutanoic acid ethyl ester 3ba.29 1H
NMR (500 MHz, CDCl3) d 7.31–7.17 (m, 5H), 4.07 (q,
J = 7.5 Hz, 2H), 3.27 (sext, J = 8.0 Hz), 2.60 (dd, J =
15, 7 Hz, 1H), 2.53 (dd, J = 15, 7 Hz, 1H), 1.30 (d,
J = 7.2 Hz, 3H), 1.17 (t, J = 7 Hz, 3H). 13C NMR
(125 MHz, CDCl3) d 172.4, 145.7, 128.4, 126.7, 126.4,
NMR (125 MHz, CDCl3) d 170.7, 142.7, 128.9, 127.2,
20
126.4, 68.6, 37.4, 37.3, 30.2. ½aꢀD ¼ þ4:4 (c 2.70, CHCl3)
20
99% ee (S) {lit.6a ½aꢀD ¼ þ4:0 (c 2.70, CHCl3) 98% ee (S)}.

S. Oi et al. / Tetrahedron: Asymmetry 17 (2006) 598–602
601
4.3.9. 3-(4-Methoxyphenyl)butanoic acid isopropyl ester
3cb.6d 1H NMR (500 MHz, CDCl3) d 7.13 (d,
J = 9 Hz, 2H), 6.83 (d, J = 9 Hz, 2H), 4.99 (sept,
J = 6.3 Hz, 1H), 3.77 (s, 3H), 3.22 (sext, J = 7.1 Hz),
2.53 (dd, J = 14.5, 7.3 Hz, 1H), 2.48 (dd, J = 14.5,
7.5 Hz, 1H), 1.27 (d, J = 7 Hz, 3H), 1.17 (d,
J = 6.5 Hz, 3H), 1.12 (d, J = 6.3 Hz, 3H). 13C NMR
4.3.15. N-Benzyl-3-(4-Methoxyphenyl)butyramide 5eb.6g
1H NMR (500 MHz, CDCl3) d 7.26–7.22 (m, 3H), 7.15–
7.12 (m, 2H), 7.02–7.00 (m, 2H), 6.85–6.80 (m, 2H), 5.49
(s, 1H), 4.38 (dd, J = 14.5, 6.3 Hz, 1H), 4.27 (dd,
J = 14.5, 5.4 Hz, 1H), 3.78 (s, 3H), 3.28 (sext,
J = 7.5 Hz, 1H), 2.45 (dd, J = 13.5, 6.5 Hz, 1H), 2.39
(dd, J = 13.5, 8.3 Hz, 1H), 1.30 (d, J = 7 Hz, 3H). 13C
NMR (125 MHz, CDCl3) d 171.5, 158.2, 138.1, 127.8,
(125 MHz, CDCl3) d 171.9, 158.0, 137.8, 127.7, 113.7,
23
67.4, 55.2, 43.5, 35.8, 22.0, 21.7, 21.7. ½aꢀD ¼ ꢁ25 (c
20
128.5, 127.7, 127.6, 127.3, 114.0, 55.2, 46.2, 43.4, 36.3,
24
0.96, CHCl3) 88% ee {lit.6d ½aꢀD ¼ ꢁ21:6 (c 0.99, CHCl3)
22.0. ½aꢀD ¼ ꢁ3:3 (c 1.04, CDCl3) 90% ee (lit.6g
20
92% ee}.
½aꢀD ¼ ꢁ11:6 (c 1.00, CDCl3) 87% ee).
4.3.10. 3-(4-Chlorophenyl)butanoic acid isopropyl ester
3cc. 1H NMR (400 MHz, CDCl3) d 7.27–7.23 (m, 2H),
7.17–7.13 (m, 2H), 4.93 (sept, J = 7.5 Hz, 1H), 3.24
(sext, J = 7.2 Hz, 1H), 2.53 (dd, J = 14.8, 7.6 Hz, 1H),
2.49 (dd, J = 14.8, 7.6 Hz, 1H), 1.26 (d, J = 7 Hz, 3H),
1.16 (dd, J = 6.2 Hz, 3H), 1.11 (dd, J = 6.2 Hz, 3H).
13C NMR (100 MHz, CDCl3) d 171.5, 144.1, 131.8,
128.5, 128.1, 67.6, 43.0, 36.0, 21.8, 21.7, 21.6. IR (neat)
4.3.16. N-Benzyl-3-(4-Chlorophenyl)butyramide 5ec.
1H NMR (400 MHz, CDCl3) d 7.30–7.22 (m, 5H),
7.15–7.12 (m, 2H), 7.02–6.98 (m, 2H), 5.61 (s, 1H),
4.40 (dd, J = 14.8, 6.4H, 1H), 4.23 (dd, J = 14.8,
5.2 Hz, 1H), 3.32 (sext, J = 8 Hz, 1H), 2.45 (dd,
J = 14, 6.8 Hz, 1H), 2.37 (dd, J = 14, 8.3 Hz, 1H), 1.29
(d, J = 7 Hz, 3H). 13C NMR (100 MHz, CDCl3) d
171.0, 144.1, 128.0, 132.1, 128.7, 128.6, 128.2, 127.5,
127.4, 45.7, 43.4, 36.5, 21.7. IR (KBr) 3309, 3081,
1730, 1261, 1108, 1013 cmꢁ1
.
Anal. Calcd for
C13H17O2Cl: C, 64.86; H, 7.12; Cl, 14.73. Found: C,
1644, 1552, 1495, 1252 cmꢁ1
C17H18NOCl: C, 70.95; H, 6.30; N, 4.87; Cl, 12.32.
.
Anal. Calcd for
23
64.60; H, 6.94; Cl, 14.60. ½aꢀD ¼ ꢁ26 (c 1.02, CHCl3)
24
93% ee.
Found: C, 70.89; H, 6.51; N, 4.73; Cl, 12.18. ½aꢀD
¼
ꢁ8:8 (c 0.99, CDCl3) 92% ee.
4.3.11.
3-Phenylbutyramide
5aa.6g 1H
NMR
(500 MHz, CDCl3) d 7.41–7.19 (m, 5H), 5.67 (s, 1H),
5.37 (s, 1H), 3.27 (sext, J = 7.1 Hz, 1H), 2.53–2.40 (m,
2H), 1.32 (d, J = 7.0 Hz, 3H). 13C NMR (125 MHz,
Acknowledgement
CDCl3) d 174.2, 145.7, 128.6, 126.7, 126.5, 44.7, 36.7,
This work was partly supported by a Grant-in-Aid
for Scientific Research from the Ministry of Education,
Culture, Sports, Science and Technology, Japan.
24
21.7. ½aꢀD ¼ ꢁ36 (c 1.01, CHCl3) 81% ee (R) {lit.6g
20
½aꢀD ¼ ꢁ30:9 (c 1.01, CHCl3) 89% ee (R)}.
4.3.12. 3-Phenylhexanamide 5ba. 1H NMR (400 MHz,
CDCl3) d 7.32–7.18 (m, 5H), 5.52 (s, 1H), 5.26 (s, 1H),
3.12–3.04 (m, 1H), 2.51 (dd, J = 14.3, 6.6 Hz, 1H),
2.44 (dd, J = 14.3, 8.4 Hz, 1H), 1.71–1.54 (m, 2H),
1.25–1.10 (m, 2H), 0.85 (t, J = 7.3 Hz, 3H). 13C
References
1. Knight, D. W. In Comprehensive Organic Synthesis; Trost,
B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991;
Vol. 3, pp 481–520.
2. Review: Sibi, M. P.; Manyem, S. Tetrahedron 2000, 56,
8033.
NMR (100 MHz, CDCl3)
127.4, 126.5, 43.8, 42.4, 38.4, 20.5, 13.9. IR (KBr)
3408, 3196, 1655, 1406 cmꢁ1
Anal. Calcd for
d 174.2, 144.2, 128.5,
.
C12H17NO: C, 75.35; H, 8.96; N, 7.32. Found: C,
3. Sakai, M.; Hayashi, H.; Miyaura, N. Organometallics
1997, 16, 4229.
24
75.16; H, 9.05; N, 7.16. ½aꢀD ¼ ꢁ29 (c 1.00, CHCl3)
4. Takaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.;
Miyaura, N. J. Am. Chem. Soc. 1998, 120, 5579.
5. Reviews: (a) Hayashi, T. Synlett 2001, 879; (b) Fagnou,
K.; Lautens, M. Chem. Rev. 2003, 103, 169; (c) Hayashi,
T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829; (d)
Hayashi, T. Bull. Chem. Soc. Jpn. 2004, 77, 13; (e)
Hayashi, T. Pure Appl. Chem. 2004, 76, 465.
91% ee.
4.3.13. N,N-Dimethyl-3-phenylbutyramide 5da.33 1H
NMR (400 MHz, CDCl3) d 7.31–7.17 (m, 5H), 3.36
(sext, J = 6.9 Hz, 1H), 2.90 (s, 3H), 2.86 (s, 3H), 2.61
(dd, J = 15, 6.2 Hz, 1H), 2.51 (dd, J = 15, 8 Hz, 1H),
1.33 (d, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3)
6. (a) Takaya, Y.; Senda, T.; Kurushima, H.; Ogasawara,
M.; Hayashi, T. Tetrahedron: Asymmetry 1999, 10, 4047;
(b) Takaya, Y.; Ogasawara, M.; Hayashi, T. Tetrahedron
Lett. 1999, 40, 6957; (c) Hayashi, T.; Senda, T.; Takaya,
Y.; Ogasawara, M. J. Am. Chem. Soc. 1999, 121, 11591;
(d) Sakuma, S.; Sakai, M.; Itooka, R.; Miyaura, N. J.
Org. Chem. 2000, 65, 5951; (e) Hayashi, T.; Senda, T.;
Ogasawara, M. J. Am. Chem. Soc. 2000, 122, 10716; (f)
Senda, T.; Ogasawara, M.; Hayashi, T. J. Org. Chem.
2001, 66, 6852; (g) Sakuma, S.; Miyaura, N. J. Org.
Chem. 2001, 66, 8944; (h) Kuriyama, M.; Tomioka, K.
Tetrahedron Lett. 2001, 42, 921; (i) Reetz, M. T.; Moulin,
D.; Gosberg, A. Org. Lett. 2001, 3, 4083; (j) Hayashi, T.;
Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am.
Chem. Soc. 2002, 124, 5052; (k) Kuriyama, M.; Nagai,
d 171.7, 146.5, 128.3, 126.8, 126.1, 41.7, 37.2, 36.4,
21
35.3, 21.5. ½aꢀD ¼ ꢁ16 (c 1.02, CHCl3) 72% ee (R)
25
(lit.33 ½aꢀD ¼ þ40:1 (c 4.66, EtOH) (S)).
4.3.14. N-Benzyl-3-phenylbutyramide 5ea.6g 1H NMR
(500 MHz, CDCl3) d 7.29–7.19 (m, 8H), 7.02–7.00 (m,
2H), 5.64 (s, 1H), 4.35 (dd, J = 14.8, 6 Hz, 1H), 4.26
(dd, J = 14.8, 5.5 Hz, 1H), 3.32 (sext, J = 7.1 Hz, 1H),
2.45 (d, J = 7.6 Hz, 2H), 1.31 (d, J = 7.1 Hz, 3H). 13C
NMR (125 MHz, CDCl3) d 171.4, 145.7, 138.1, 128.6,
128.5, 127.5, 127.3, 126.8, 126.4, 45.8, 43.4, 37.0, 21.8.
20
20
½aꢀD ¼ ꢁ13 (c 1.01, CDCl3) 92% ee (lit.6g ½aꢀD ¼ ꢁ12:1
(c 1.00, CDCl3) 93% ee).

602
S. Oi et al. / Tetrahedron: Asymmetry 17 (2006) 598–602
K.; Yamada, K.-i.; Miwa, Y.; Taga, T.; Tomioka, K. J.
16. (a) Yamamoto, K.; Suzuki, S.; Tsuji, J. Tetrahedron Lett.
1980, 21, 1653; (b) Eaborn, C.; Griffiths, R. W.; Pidcock,
A. J. Organomet. Chem. 1982, 225, 331; (c) Matsumoto,
H.; Kasahara, M.; Takahashi, M.; Arai, T.; Nakao, T.;
Nagai, Y. J. Organomet. Chem. 1983, 250, 99; (d)
Hatanaka, Y.; Hiyama, T. Tetrahedron Lett. 1987, 28,
4715.
17. (a) Murata, M.; Suzuki, K.; Watanabe, S.; Masuda, Y. J.
Org. Chem. 1997, 62, 8569; (b) Murata, M.; Watanabe, S.;
Masuda, Y. Tetrahedron Lett. 1999, 40, 9255; (c) Manoso,
A. S.; DeShong, P. J. Org. Chem. 2001, 66, 7449; (d)
Murata, M.; Ishikura, M.; Nagata, M.; Watanabe, S.;
Masuda, Y. Org. Lett. 2002, 4, 1843.
Am. Chem. Soc. 2002, 124, 8932; (l) Amengual, R.;
Michelet, V.; Geneˆt, J.-P. Synlett 2002, 1791; (m)
Pucheault, M.; Darses, S.; Geneˆt, J.-P. Tetrahedron
Lett. 2002, 43, 6155; (n) Pucheault, M.; Darses, S.;
Geneˆt, J.-P. Eur. J. Org. Chem. 2002, 3552; (o) Shi, Q.;
Xu, L.; Li, X.; Jia, X.; Wang, R.; Au-Yeung, T. T.-L.;
Chan, A. S. C.; Hayashi, T.; Cao, R.; Hong, M.
Tetrahedron Lett. 2003, 44, 6505; (p) Boiteau, J.-G.;
Imbos, R.; Minnaard, A. J.; Feringa, B. L. Org. Lett.
2003, 5, 681, and Org. Lett. , 52003, 1385, for correc-
tions; (q) Boiteau, J.-G.; Minnaard, A. J.; Feringa, B. L.
J. Org. Chem. 2003, 68, 9481; (r) Ma, Y.; Song, C.; Ma,
C.; Sun, Z.; Chai, Q.; Andrus, M. B. Angew. Chem., Int.
Ed. 2003, 42, 5871.
18. Oi, S.; Moro, M.; Inoue, Y. Organometallics 2001, 20,
1036.
7. (a) Hayashi, T.; Tokunaga, N.; Yoshida, K.; Han, J. W.
J. Am. Chem. Soc. 2002, 124, 12102; (b) Yoshida, K.;
Hayashi, T. J. Am. Chem. Soc. 2003, 125, 2872.
8. Kakuuchi, A.; Taguchi, T.; Hanzawa, Y. Tetrahedron
2004, 60, 1293.
9. Oi, S.; Sato, T.; Inoue, Y. Tetrahedron Lett. 2004, 45,
5051.
10. Shintani, R.; Tokunaga, N.; Doi, H.; Hayashi, T. J. Am.
Chem. Soc. 2004, 126, 6240.
19. Huang, T. S.; Li, C. J. Chem. Commun. 2001, 2348.
20. (a) Mori, A.; Danda, Y.; Fujii, T.; Hirabayashi, K.;
Osakada, K. J. Am. Chem. Soc. 2001, 123, 10774; (b) Fujii,
T.; Koike, T.; Mori, A.; Osakada, K. Synlett 2002, 298; (c)
Koike, T.; Du, X.; Mori, A.; Osakada, K. Synlett 2002,
301.
21. Oi, S.; Honma, Y.; Inoue, Y. Org. Lett. 2002, 4, 667.
22. Murata, M.; Shimazaki, R.; Ishikura, M.; Watanabe, S.;
Masuda, Y. Synthesis 2002, 717.
11. (a) Oi, S.; Moro, M.; Ono, S.; Inoue, Y. Chem. Lett. 1998,
83; (b) Venkatraman, S.; Meng, Y.; Li, C. J. Tetrahedron
Lett. 2001, 42, 4459; (c) Huang, T. S.; Li, C. J. Org. Lett.
2001, 3, 2037; (d) Oi, S.; Moro, M.; Ito, H.; Honma, Y.;
Miyano, S.; Inoue, Y. Tetrahedron 2002, 58, 91.
12. Hayashi, T.; Ueyama, K.; Tokunaga, N.; Yoshida, K. J.
Am. Chem. Soc. 2003, 125, 11508.
13. (a) Ojima, I.; Li, Z.; Zhu, J. In The Chemistry of
Organosilicon Compounds; Rappoport, S., Apeloig, Y.,
Eds.; Wiley: New York, 1998; (b) Langkopf, E.; Schinzer,
D. Chem. Rev. 1995, 95, 1375.
14. (a) Ojima, I.; Kumagai, M.; Nagai, Y. J. Organomet.
Chem. 1974, 66, C14; (b) Hill, J. E.; Nile, T. A. J.
Organomet. Chem. 1977, 137, 293; (c) Watanabe, H.;
Kitahara, T.; Motegi, T.; Nagai, Y. J. Organomet. Chem.
1977, 139, 215; (d) Tanke, R. S.; Crabtree, R. H. J. Am.
Chem. Soc. 1990, 112, 7984; (e) Ojima, I.; Clos, N.;
Donovan, R. J.; Ingallina, P. Organometallics 1990, 9,
3127; (f) Takeuchi, R.; Tanouchi, N. J. Chem. Soc., Perkin
Trans. 1 1994, 2909; (g) Takeuchi, R.; Nitta, S.; Watanabe,
D. J. Org. Chem. 1995, 60, 3045; (h) Mori, A.; Takahisa,
E.; Kajiro, H.; Hirabayashi, K.; Nishihara, Y.; Hiyama, T.
Chem. Lett. 1998, 443; (i) Na, Y.; Chang, S. Org. Lett.
2000, 2, 1887; (j) Faller, J. W.; D’Alliessi, D. G. Organo-
metallics 2002, 21, 1743; (k) Katayama, H.; Taniguchi, K.;
Kobayashi, M.; Sagawa, T.; Minami, T.; Ozawa, F. J.
Organomet. Chem. 2002, 645, 192.
23. Oi, S.; Taira, A.; Honma, Y.; Inoue, Y. Org. Lett. 2003, 5,
97.
24. Otomaru, Y.; Hayashi, T. Tetrahedron: Asymmetry 2004,
15, 2647.
25. (a) Hishikata, T.; Yamamoto, Y.; Miyaura, N. Chem.
Lett. 2003, 32, 752; (b) Denmark, S. E.; Amishiro, N. J.
Org. Chem. 2003, 68, 6997; (c) Hishikata, T.; Yamamoto,
Y.; Miyaura, N. Organometallics 2004, 23, 4317; (d)
Hishikata, T.; Yamamoto, Y.; Gridnev, I. D.; Miyaura, N.
Organometallics 2005, 24, 5025.
26. (a) Green, M.; Kuc, T. A.; Taylor, S. H. J. Chem. Soc. (A)
1971, 2334; (b) Oi, S.; Moro, M.; Fukuhara, H.; Kawa-
nishi, T.; Inoue, Y. Tetrahedron 2003, 59, 4351.
27. Barton, P.; Laws, A. P.; Page, M. I. J. Chem. Soc., Perkin
Trans. 2 1994, 2021.
28. Hirose, K.; Naka, H.; Yano, M.; Ohashi, S.; Naemura, K.;
Tobe, Y. Tetrahedron: Asymmetry 2000, 11, 1199.
29. Yang, H.; Henke, E.; Bornscheuer, U. T. J. Org. Chem.
1999, 64, 1709.
30. (a) Yamamoto, K.; Ikeda, K.; Yin, L. K. J. Organomet.
Chem. 1989, 370, 319; (b) Tsuchiya, Y.; Kanazawa, Y.;
Shiomi, T.; Kobayashi, K.; Nishiyama, H. Synlett 2004,
2493.
31. Ono, N.; Kamimura, A.; Miyake, H.; Hamamoto, I.; Kaji,
A. J. Org. Chem. 1985, 50, 3692.
32. Cram, D. J.; Nyquist, H. L.; Abd Elhafez, F. A. J. Am.
Chem. Soc. 1957, 2876.
15. Trost, B. M.; Ball, Z. T. J. Am. Chem. Soc. 2001, 123,
12726.
33. Bussas, R.; Munsterer, H.; Kresze, G. J. Org. Chem. 1983,
48, 2828.