Asymmetric Synthesis of Chiral 1,3-Disubstituted Allylsilanes via Copper(I)-Catalyzed 1,4-Conjugate Silylation of α,β-Unsaturated Sulfones and Subsequent Julia-Kocienski Olefination

Article abstract of DOI:10.1002/cjoc.202100101

A general synthesis of chiral 1,3-disubstituted allylsilanes is established through copper(I)-catalyzed asymmetric 1,4-conjugate silylation of α,β-unsaturated sulfones and subsequent Julia-Kocienski olefination. By modification of McQuade's NHC ligand, the catalytic asymmetric conjugate silylation with a broad substrate scope is achieved in high enantioselectivity. The following Julia-Kocienski olefination proceeds smoothly at room temperature to deliver an array of chiral allylsilanes in moderate yields. More interestingly, a one-pot asymmetric synthesis with high synthetic efficiency is successfully realized. Utility of the prepared chiral 1,3-disubsituted allylsilanes is demonstrated in the asymmetric allylation of both aldehyde and aldimine. Finally, an interesting “match and mismatch” phenomenon is observed in the asymmetric allylation of chiral aldehydes.

Full text of DOI:10.1002/cjoc.202100101

Chinese Journal
of Chemistry
CJC
中 国 化 学 - An International Journal
Accepted Article
Title: Asymmetric Synthesis of Chiral 1,3-Disubstituted Allylsilanes via Copper(I)-
Catalyzed 1,4-Conjugate Silylation of α,β-Unsaturated Sulfones and Subsequent
Julia-Kocienski Olefination
Authors: Xian-Liang Wang, Xing-Hao Yin, Jun-Zhao Xiao Xue-Shun Jia, and Liang
Yin*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2021, 39, 10.1002/cjoc.202100101.
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published online in Early View: http://dx.doi.org/10.1002/cjoc.202100101.
ISSN 1001-604X • CN 31-1547/O6
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Yin Liang (Orcid ID: 0000-0001-9604-5198)
Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Asymmetric Synthesis of Chiral 1,3-Disubstituted Allylsilanes via
Copper(I)-Catalyzed 1,4-Conjugate Silylation of α,β-Unsaturated
Sulfones and Subsequent Julia-Kocienski Olefination
Xian-Liang Wang,a,b Xing-Hao Yin,a Jun-Zhao Xiao,a Xue-Shun Jia,b and Liang Yin*,a
a CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of
Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
b Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, China
Keywords
Chiral Allylsilanes | Silylation | Julia–Kocienski Olefination | Allylation | Asymmetric Catalysis
Main observation and conclusion
A general synthesis of chiral 1,3-disubstituted allylsilanes is established through copper(I)-catalyzed asymmetric 1,4-conjugate silyla-
tion of α,β-unsaturated sulfones and subsequent Julia-Kocienski olefination. By modification of McQuade’s NHC ligand, the catalytic
asymmetric conjugate silylation with a broad substrate scope is achieved in high enantioselectivity. The following Julia–Kocienski ole-
fination proceeds smoothly at room temperature to deliver an array of chiral allylsilanes in moderate yields. More interestingly, a
one-pot asymmetric synthesis with high synthetic efficiency is successfully realized. Utility of the prepared chiral 1,3-disubsituted al-
lylsilanes is demonstrated in the asymmetric allylation of both aldehyde and aldimine. Finally, an interesting “match and mismatch”
phenomenon is observed in the asymmetric allylation of chiral aldehydes.
Comprehensive Graphic Content
mol
NaOEt/NaOMe
NHC-4-CuCl
%)
(5
PhMe
O
S
2Si
O
S
S
N
S
N
PhMe2
Si
Bpin
o
R
R
MTBE,
h
60
-30
C,
O
O
R'CHO
LDA
equiv)
equiv)
(1.5
(3.0
THF, rt, 2 h
=
E/Z >20/1
or
equiv)
R''CXH
O
NBoc)
(X=
Ph
TiCl
Ph
SiMe2
4 (2
R"
XH
Me
CH Cl -60 oC
,
2
R
R'
2
=
=
Me, R' Ph
R
chiral
1,3-disubstituted
allylsilanes
This article has been accepted for publication and undergone full peer review but has not been
through the copyediting, typesetting, pagination and proofreading process which may lead to
differences between this version and the Version of Record. Please cite this article as doi:
10.1002/cjoc.202100101
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First author et al.
Report
jugate addition of PhMe2SiBpin[36-37] to cyclic enones and lactones
with high enantioselectivity.[38-39] Later, the substrate scope was
extended to linear (Z)-α,β-unsaturated compounds with Rh(I) cat-
alyst and (E)-alkenes activated by azaaryl groups with copper(I)
catalyst.[39-44] In 2010, the Hoveyda Group reported a NHC-Cu
complex-catalyzed conjugate silylation of α,β-unsaturated carbon-
yl compounds with PhMe2SiBpin.[45] Subsequently, the catalytic
system was extended to α,β,γ,δ-unsaturated carbonyl com-
pounds.[30] In the dienones and dienolates with a locked β-position,
1,6-addtion occurred to give chiral allylsilanes with high enanti-
oselectivity (Scheme 1a). In 2013, Procter further advanced the
copper(I) catalytic system to α,β-unsaturated lactones, lactams
and amides.[46-47] Moreover, such a conjugate silylation with either
NHC catalysis by Hoveryda,[48-49] or dual catalysis by Córdova,[50] or
copper(II) catalysis by Kobayashi[51] and by Xu[34] was developed.
However, catalytic asymmetric conjugate silylation of
α,β-unsaturated sulfones has never been investigated.
It is obvious that the products of above silylation could be
suitable starting materials of Julia olefination, which would lead to
the generation of chiral 1,3-disubstituted allylsilane reagents. Con-
sidering the convenience to implement the Julia olefination, it
would be judicious to employ α,β-unsaturated benzothiazole (BT)
sulfones as the substrates for the copper(I)-catalyzed asymmetric
silylation, which would produce chiral BT-sulfones containing a
silyl group (Scheme 1b). The subsequent Julia-Kocienski olefina-
tion with various aldehydes would allow the smooth generation of
diverse chiral allylsilanes containing both C1-subsitutent and
C3-substituent. Furthermore, it would be idea to perform such a
strategy in a one-pot fashion to achieve high synthetic efficiency.
Background and Originality Content
Allylation of aldehydes, ketones, and imines has been viewed
as one of the most important weapons in the arsenal of organic
synthesis, which leads to synthetically versatile homoallylic alco-
hols and homoallylic amines with high and predictable selectivity.[1]
Moreover, asymmetric induction is well achieved by virtue of easi-
ly available enantioenriched allylmetal reagents or powerful chiral
catalysts.[1] Among the various chiral allylmetal reagents, al-
lylsilanes are very appealing as they are successfully employed in a
variety of highly stereoselective reactions.[2-4] For example, the
Hosomi-Sakurai reaction[5-7] involves Lewis acid-promoted allyla-
tion of various electrophiles with chiral allylsilanes. The availability
of chiral allylsilanes greatly advances the preparation of syntheti-
cally powerful homoallylic alcohols and homoallylic amines with
excellent transfer of chirality.[1-4]
In view of the importance of chiral allylsilanes in organic syn-
thesis, significant efforts have been dedicated to their preparation.
Classically, multistep synthesis is required for the preparation of
enantioenriched allylsilanes. Recently, new strategies with high
synthetic efficiency have been emerging. Basically, these strategies
are classified into two types, including transformations with or-
ganic molecules bearing a pre-installed silyl group[8-21] or introduc-
tions of silicon to organic compounds[22-34]. In the latter cases, the
simultaneous induction of chirality and silicon species under
asymmetric catalysis is particularly abstracting due to the higher
synthetic efficiency. However, most of the reported methodologies
were limited to the asymmetric synthesis of chiral allylsilanes
without C3-substituent or specific 1,3-disubstituted allylsilanes
(Scheme 1a). Reisman reported a new and efficient synthesis of
enantioenriched 1,3-disubstituted allylsilanes via Ni-catalyzed
reductive cross-coupling.[33] However, C1-substituent was limited
to aryl groups. Therefore, methodologies for the preparation of
chiral 1,3-disubstituted allylsilanes with broader substrate scope
are still highly desirable.
Results and Discussion
Results (sample title, optional)
As shown in Table 1, the model reaction of PhMe2SiBpin and
α,β-unsaturated BT-sulfone 2a was investigated for the optimiza-
tion of reaction conditions. In the presence of 5 mol % CuCl, 5 mol %
(R)-TOL-BINAP, 30 mol % NaOtBu, and 2 equiv MeOH, the conju-
gate silylation occurred smoothly to give the product 3a in 75%
yield with 24% ee (entry 1). Unfortunately, the exhaustive screen-
ing of commercially available bisphosphines did not lead to signif-
icantly increased enantioselectivity. The highest asymmetric in-
duction (38% ee) was observed in the reaction with (R,R)-Ph-BPE
as the ligand (entry 2). Then, we turned our attention from phos-
phines to NHC ligands. The reaction with NHC-1 (one of Mauduit’s
NHCs)[52-55] afforded 3a in 99% yield. However, the enantioselec-
tivity was completely lost (entry 3). Moreover, NHC-2 (one of
Hoveyda’s NHCs)[56] led to slightly increased enantioselectivity
(entry 4).
Scheme 1 Reported Asymmetric Synthesis of Chiral 1,3-Disubstituted
Allylsilanes and Our Synthetic Strategy
Chiral
Constructed through Introduction of Silicon
Species
(a)
Allylsilanes
SiCl3
1
O
SiMe2Ph
SiMe2Ph
PhMe2Si
R
X
SiMe2Ph
R
n
3
R
R
Me
3
MeOOC
1
3
1
3
1
3
1
=
2)
1,
(n
Bpnd*
Bpin
Davies, Panek
1997, 2010
Hoveyda
2012
Hayashi
2001
Suginome
2003, 2006
Suginome
2006
O
Si
1
Me Ph
OH SiMe2Ph
SiMe2Ph
SiR3
Ar
PhMe2Si
Ar
Ar'
NHPG
2
R
R'
X
R
R
R
3
3
1
3
1
3
1
1
3
R'
and
2012
Hoveyda
2012
Saito
Sato
Oestreich
2013, 2015
Reisman
2018
Xu
2018
With NHC-3 (McQuade’s six-membered NHC),[57-60] the enan-
tioselectivity was further increased to 26% ee but with decreased
yield (entry 5). To our joy, the reaction with ent-NHC-4, a newly
prepared six-membered NHC with bigger steric hindrance, pro-
vided 3a in 55% yield with significantly enhanced enantioselectivi-
ty (60% ee) (entry 6). The use of copper(I)-NHC-4 complex further
promoted the enantioselectivity to 70% ee, indicating the ad-
vantage of using preformed complex over employing complex
generated in situ (entry 7). Higher enantioselectivity (78% ee)
was observed at -20 oC (entry 8). At -20 oC, replacing THF with
of Chiral
Asymmetric Conjugate Silylation
through
Copper(I)-Catalyzed
1,3-Disubsituted
(b) Asymmetric Synthesis
Allylsilanes
and
Julia-Kocienski Olefination
Subsequent
O
PhMe2Si
[Cu]
O
S
S
N
S
N
PhMe2SiBpin
S
*
R
R
base
O
O
base
Julia-Kocienski
Olefination
R'CHO
X
R'
SiMe2Ph
*
R''
H
t
*
MTBE (methyl butyl ether) and employing 0.5 equiv NaOtBu re-
R''
*
R
R
R'
1
3
or
aldehyde
aldimine
allylation
HX
H
sulted in further rising in both yield and enantioselectivity (66%,
88% ee) (entry 9). By setting the reaction at -30 oC, slight increases
in both yield and enantioselectivity were obtained (70%, 92% ee)
(entry 10). NaOEt showed superior effect to NaOtBu and led to 88%
yield with maintained enantioselectivity (entry 11). The reaction
with 2 equiv PhMe2SiBpin gave 3a in excellent yield with main-
tained enantioselectivity (entry 12). Definitely, our new NHC-Cu(I)
versatile
intermediates
chiral
allylation
asymmetric
reagents
synthetic
Catalytic asymmetric conjugate addition of silicon-species to
α,β-unsaturated compounds is a highly efficient method to pre-
pare stereogenic carbon centers containing a silyl group.[35] In
2006, Oestreich and co-workers uncovered a Rh(I)-catalyzed con-
www.cjc.wiley-vch.de
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem. 2021, 39, XXX－XXX

Running title
Chin. J. Chem.
complex would be an excellent complement to the famous
McQudade’s NHC-copper(I) complex in asymmetric catalysis.
thioether (2o) were suitable substrates, which were transformed
to the corresponding products (3i-3o) consistently in high yields
(80%-97%) with high enantioselectivity (85%-96% ee). In the reac-
tion with 2k, lower reaction temperature was needed to improve
the enantioselectivity. Clearly, good tolerance of the above func-
tional groups at present reaction conditions was very appealing as
these functional groups would allow facile further structure elab-
oration.
Table 1 Optimization of the Reaction Conditionsa
mol
mol
mol
CuCl
ligand (5
base
(x
%)
%)
%)
(5
SiMe2Ph
SO2BT
S
N
PhMe2SiBpin
1
SO2BT
*
THF, T o t h
C,
Me
Me
2a
3a
BT
Table 2 Substrate Scope of α,β-Unsaturated BT-Sulfones 2a
Entry
Ligand
Base, x
NaOtBu,
T
t
Yield (%)b Ee (%)c
mol
NHC-4-CuCl
base
%)
equiv)
(5
(x
SiMe2Ph
SO2BT
PhMe2SiBpin
1
SO2BT
1d
2d
3
(R)-TOL-BINAP
(R,R)-Ph-BPE
NHC-1
rt
12
75
30
99
96
57
55
47
42
66
70
-24
38
-2
MTBE, -30 o 60 h
R
R
C,
30
NaOtBu,
30
2
3
rt
rt
12
12
12
12
12
12
48
48
48
=
base NaOEt
equiv)
(0.5
NaOtBu,
,
=
=
=
=
=
=
=
=
ee
ee
eeb,c
ee
R
R
R
R
R
R
R
R
Me 3a
92%
, 96%,
ee
Et 3b
92%
93%
, 99%,
92%
, 94%,
,
, 92%,
SiMe2
Ph
nBu 3c
10
NaOtBu,
10
,
SO2BT
SiMe2Ph
iPr 3d
,
2
iBu 3e
93%
, 82%,
SO2BT
,
4
NHC-2
rt
-11
26
-60
70
78
88
92
R
ee
CH CH Ph 3f
91%
90%
, 91%,
91%
, 81%,
,
, 97%,
ee
94%
, 90%,
2
2
3i
c
eeb
eec
3g
,
pentyl
chexyl 3h
NaOtBu,
,
5
NHC-3
rt
10
NaOtBu,
10
nBu
SiMe2Ph
SiMe2Ph
SO2BT
SiMe2Ph
SO2BT
SO2BT
6
ent-NHC-4
NHC-4-CuCl
NHC-4-CuCl
NHC-4-CuCl
NHC-4-CuCl
rt
BzO
TBSO
3
3
3
NaOtBu,
ee
eed
ee
94%
3j
3k
3l
, 80%,
85%
91%, 91%
, 97%,
,
7e
8e
9e,f
10e,f
rt
10
NaOtBu,
10
SiMe2Ph
SiMe2Ph
SO2BT
SiMe2Ph
SO2BT
SO2BT
-20
-20
-30
Cl
Br
PhS
3
4
4
NaOtBu,
ee
ee
ee
91%
3m
3n
3o
F
96%
85%, 91%
, 95%,
,
, 90%,
50
NaOtBu,
50
=
base NaOMe
equiv)
(1.0
SiMe2Ph
SO2BT
=
ee
93%
, 98%,
R
H
,
3p
=
=
=
=
=
=
=
=
=
=
ee
ee
R
R
R
R
R
R
R
R
R
R
Me
3q
,
,
,
99%, 88%
92%
, 89%,
tBu 3r
11e,f
12e,f,g
NHC-4-CuCl
NHC-4-CuCl
-30
-30
48
60
88
96
92
92
NaOEt, 50
ee
OMe 3s
85%
,
, 80%,
, 88%,
SiMe2Ph
SO2BT
ee
SMe 3t
89%
86%
83%
, 93%,
,
ee
71%
3aa
, 78%,
NaOEt, 50
ee
ee
OCF3 3u
,
, 96%,
OCF H 3v
,
SiMe2Ph
2
a (1: 0.15 mmol, 2a: 0.1 mmol.) (Determined by 1H NMR analysis of reac-
tion crude mixture using mesitylene as an internal standard.) (Deter-
mined by chiral-stationary-phase HPLC analysis.) d (2 equiv MeOH used.) e
(NHC-4-CuCl used directly.) (MTBE used instead of THF.) (2 equiv
PhMe2SiBpin used.)
b
eec
R
OCH CH Cl 3w
93%
,
, 78%,
ee
ee
ee
2
2
F
SO2BT
F
3x
, 94%,
91%
82%
,
c
Br 3y
,
, 99%,
CF3 3z
83%
,
,
81%,
ee
, 83%, 80%
3ab
f
g
SiMe2Ph
SO2BT
SiMe2Ph
SO2BT
SiMe2Ph
SO2BT
Ph
Ph
Ph
O
BocN
3ae
Ph
PTol2
PTol2
N
N
P
N
N
ee
ee
ee
86%
P
,
3ac
, 92%,
3ad
,
92%
73%, 85%
reported.
, 82%,
PF6
Ph
HO
SO3
NHC-2
Ph
a
:
mmol,
:
2
0.2
mmol.
was
b1
was
1
0.4
Isolated
The enantioselectivity
determined
yield
R
R R
NHC-1
(
)-TOL-BINAP
(
)-Ph-BPE
o
used. c
chiral-stationary-phase HPLC
NaOEt
72 h. d-40
84 h.
C,
equiv
by
analysis.
Subsequently, the substrate scope investigation was extended
N
N
N
Et
Et
Ph
Ph
Ph
from β-alkyls to β-aryls by changing 0.5 equiv NaOEt to 1.0 equiv
NaOMe (for the optimization details, see SI). The reaction of
β-phenyl-α,β-unsaturated sulfone (2p) generated product 3p in 98%
yield with 93% ee. As for para-substituents on the phenyl, both
electron-donating groups (3q-3w) and electron-withdrawing
groups (3x-3z) were well accepted with both high yields (78%-99%)
and high enantioselectivity (82%-93% ee). However, the silylation
was sensitive to the substitution pattern on the phenyl group as
only moderate enantioselectivity (71% ee) was obtained in the
reaction of β-othro-F-phenyl-α,β-unsaturated BT-sulfone (2aa). In
the case of β-meta-F-phenyl-α,β-unsaturated BT-sulfone (2ab),
product 3ab was isolated in 83% yield with 80% ee. Moreover,
2-naphthyl (2ac), 2-furanyl (2ad), and 1-N-Boc-indolyl (2ae) were
also acceptable at the β-position and the corresponding products
(3ac-3ae) were furnished in moderate to high yields (73%-92%)
and high enantioselectivity (85%-92% ee). Generally speaking, the
N
N
N
N
N
N
BF4 Ph
BF4 Ph
Ph
CuCl
Et
Et
-
ent
NHC-3
NHC-4
NHC-4-CuCl
Under the optimized reaction conditions, the substrate scope
of α,β-unsaturated sulfones was investigated as shown in Table 2.
Various β-alkyls, including Me (2a), Et (2b), Bu (2c), Pr (2d), Bu
n
i
i
c
c
(2e), CH2CH2Ph (2f), pentyl (2g), and hexyl (2h) were well toler-
ated no matter how big the group is. However, in the cases of 2d
and 2g, 1 equiv NaOEt was required to get higher yield. The cor-
responding products (3a-3h) were generated uniformly in high
yields (81%-99%) with high enantioselectivity (90%-93% ee).
Moreover, BT-sulfones containing β-alkyls bearing various func-
tional groups, such as terminal olefin (2i), internal alkyne (2j), es-
ter (2k), silyl ether (2l), alkyl chloride (2m), alkyl bromide (2n), and
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de

First author et al.
Report
present conjugate silylation delivered the products in both high
yields and high enantioselectivity.
completed, the volatiles in the reaction mixture were evaporated
to give the crude product, which was subjected to the reaction
conditions of Julia-Kocienski olefination. To our joy, chiral al-
lylsilane 5aa was obtained in 62% yield with 92% ee. Then, the
asymmetric allylation of aldehyde and aldimine was investigated
(Scheme 3). In the presence of 2 equiv TiCl4, the allylation of iso-
butyl aldehyde (4c) and phenylpropyl aldehyde (4g) led to
homoallylic alcohols 6aac and 6aag in moderate yields with high
enantioselectivity. Interestingly, the precursor of N-Boc-aldimine
could be directly used in the TiCl4-promoted asymmetric allylation.
The reaction of 5aa and 7a furnished homoallylic amine 8aaa in 58%
yield with >20/1 dr and 86% ee. The absolute configurations of
6aac, 6aag, and 8aaa were determined tentatively in light of a
reported empirical rule.[2] The absolute configuration of 8aaa was
further confirmed by its X-ray crystallographic analysis (for the
details, see SI), which indicated the validity of the reported empir-
ical rule. Moreover, the six-membered ring transition state en-
sured the high asymmetric induction in the TiCl4-promoted allyla-
tion.[2]
Table 3 Substrate Scope of the Julia-Kocienski Olefinationa
Ph
SiMe2
O
LDA
Ph
SiMe2
5
equiv)
(3
BT
SO2
R
R'
H
THF, rt, 2 h
>20/1 E/Z
R
R'
3
4
=
5aa
R' Ph
66%
,
,
Ph
Ph
SiMe2
SiMe2
=
=
=
5ab
5ae
65%
,
5af
70%
,
R' 2-thienyl
51%
R
R
CH3
,
,
,
R' iPr
52%b
Ph
,
=
5ac
,
,
Me
R'
Me
R'
R' chexyl
66%c
,
=
5ad
,
=
=
=
R
R
R
Et 5ba 73%
,
,
Ph
Ph
SiMe2
SiMe2
iBu
75%
,
5ea
,
chexyl 5ha 70%
R
Ph
Ph
,
,
5ia
73%
,
Ph
Ph
SiMe2
SiMe2
TBSO
Ph
Cl
Ph
Scheme 3 Asymmetric Allylation of Aldehyde and Aldimine
5la
5ma
,
75%
58%
of
,
SiMe2Ph
Ph
ee
O
Ph
TiCl
equiv)
4 (2
a
:
3
:
4
mmol,
mmol.
was
ee
The
reported.
C
are
products
0.2
0.3
Isolated
values
=
the
yield
CH2Cl2 -60 o 12 h
Me
Me
H
Me
,
assumed
C,
to be unchanged in the
olefination.
b-20 o to rt. 12 h. E Z
/
4/1. C
c-40 o to rt. 12 h.
OH
=
E/Z 6.5/1.
5aa
,
4c
6aac
92%
1.5
1.5
,
equiv
ee
ee
51%, >20/1 dr, 87%
Then, the optimization of Julia-Kocienski olefination of 3a was
performed (for the details, see SI), which identified 3 equiv LDA in
THF at room temperature as the best. The olefination of 3a with
aromatic aldehyde (4a) and heteroaromatic aldehyde (4b) pro-
duced 1,3-disubstituted allylsilanes 5aa and 5ab in moderate
yields but with excellent control of the double bond geometry.
Unfortunately, the reaction of 3a with aliphatic aldehydes (4c and
4d) delivered 5ac and 5ad in moderate yields and moderate (E)/(Z)
SiMe2Ph
Ph
ee
O
Ph
TiCl
equiv)
4 (2
Ph
CH2Cl2 -60 o 12 h
Ph
H
Me
,
C,
OH
5aa
,
4g
6aag
92%
,
equiv
68%, >20/1 dr, 86%
SiMe2Ph
Ph
NHBoc
SO2Ph
Ph
TiCl
equiv)
4 (2.5
CH2Cl2 -60 o
Me
Me
12 h
C,
,
o
o
NHBoc
ratio even at lower reaction temperature (-20 C for 4c and -40 C
for 4d). The olefination with α,β-unsaturated aldehydes (4e and 4f)
also proceeded in moderate yields but with excellent (E)/(Z) ratio.
Three BT-sulfones (3b, 3e, and 3h) with alkyls other than methyl
were also subjected to the present olefination conditions, which
were transformed to the corresponding allylsilanes (5ba, 5ea, and
5ha) in moderate yields with excellent control of the double bond
geometry. Notably, three chiral BT-sulfones (3i, 3l, and 3m) con-
taining functional groups also served as competent substrates to
give the products (5ia, 5la, and 5ma) in moderate yields with ex-
cellent (E)/(Z) ratio. The Julia-Kocienski olefination apparently
proceeded without racemization and thus the ee values of the
products were assumed to be unchanged. Moreover, the absolute
configuration of 5ba was determined to be S by comparison of its
optical rotation value with a reported data (for the details, see
SI).[27] The absolute configurations of other allylsilanes (5), as well
as the products (3) in the asymmetric conjugate silylation were
then assigned tentatively. Evidently, our method provided a very
general synthetic method to access 1,3-disubsitituted allylsilanes
with both aryl and alkyl tolerated in either R or R′.
ee
5aa
,
7a
,
8aaa
58%, >20/1 dr, 86%
92%
1.5
equiv
ee
8aaa
CCDC 2020454
Chiral aldehyde 4h and its enantiomer ent-4h were prepared in
high enantioselectivity (for the details, see SI). Then, allylsilane
5aa and aldehyde 4h were subjected to TiCl4-promoted asymmet-
ric allylation (Scheme 4), which afforded chiral homoallylic alcohol
9aah in 16/1 dr. The pure major diastereoisomer was isolated in
62% yield with excellent both diastereo- and enantioselectivities.
The asymmetric allylation of ent-4h with 5aa proceeded in inferior
diastereoselectivity. Fortunately, 10aah was isolated in 47% yield
with >20/1 dr and >99% ee. Moreover, ent-5aa was synthesized by
using (R,R)-NHC ligand. As shown in Scheme 4, ent-10aah was
generated in 4/1 dr and >99% ee and ent-9aah was produced in
8/1 dr and >99% ee. Satisfactorily, both ent-10aah and ent-9aah
were isolated in >20/1 dr. Obviously, an interesting “match and
Scheme 2 One-Pot Asymmetric Synthesis of 5aa
mol
NHC-4-CuCl
NaOEt
%)
equiv)
PhCHO
LDA
equiv)
equiv)
(5
(1.5
(3.0
SiMe2
5aa
Ph
Ph
(0.5
PhMe2SiBpin
1
SO2BT
MTBE, -30 o 60 h
THF, rt, 2 h
Me
C,
Me
=
E/Z >20/1
2a
ee
62%, 92%
Instead of the synthesis with two separate reactions, a one-pot
synthesis with higher synthetic efficiency was also tried (Scheme
2). When the copper(I)-catalyzed asymmetric conjugate silylation
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© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
Chin. J. Chem. 2021, 39, XXX－XXX

Running title
Chin. J. Chem.
mismatch” phenomenon was observed in these experiments. The
absolute configurations of 9aah, ent-9aah, 10aah and ent-10aah
were assigned tentatively according to a reported empirical rule.[2]
Under the present reaction conditions with Lewis acid,
α-epimerization of the chiral aldehydes was not observed.
was charged with NHC-4-CuCl (5.4 mg, 0.01 mmol, 0.05 equiv),
NaOMe (10.8 mg, 0.2 mmol, 1.0 equiv) and α,β-unsaturated sul-
fone (0.2 mmol, 1.0 equiv) in glove box under Ar atmosphere.
Anhydrous MTBE (4.0 mL) was added via a syringe. After cooling
to -30oC, dimethylphenylsilyl boronic ester (109 μL, 0.4 mmol, 2.0
equiv) was added slowly. The resulting reaction mixture was
stirred at -30oC for 60 hours. Then the reaction mixture was
quenched by acetic acid (1.0 mL, 0.2 M in DCM). The mixture was
stirred for additional 10 minutes at -30oC and then the solvent was
removed under reduced pressure at room temperature. The resi-
due was purified by silica gel column chromatography (petroleum
ether/ethyl acetate = 9:1 to 4:1) to give the desired product.
Scheme 4 The “Match and Mismatch” Phenomenon in the Asymmetric
Allylation of α-Chiral Aldehydes
SiMe2Ph
Ph
ee
O
Ph Me
TiCl
equiv)
4 (2
Ph
CH2Cl2 -60 o 24 h
Me
Me
H
Me
Ph
,
C,
Me
OH
ee,
5aa
,
4h
92%
>99%
1.5
9aah
,
16/1 dr
1H NMR)
(crude
62%, >20/1 dr, >99%
,
equiv
ee
SiMe2Ph
Ph
ee
O
Ph Me
TiCl
Supporting Information
equiv)
4 (2
Ph
CH2Cl2 -60 o 24 h
H
Me
10aah
Ph
,
C,
Me
ee,
OH
1H NMR)
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
ent-
5aa
,
4h
98%
,
92%
1.5
8/1 dr
,
equiv
(crude
ee
47%, >20/1 dr, >99%
SiMe2Ph
Ph
ee
O
Ph Me
TiCl
equiv)
4 (2
Ph
Acknowledgement
CH2Cl2 -60 o 24 h
Me
H
Me
10aah
Ph
,
C,
Me
OH
1H NMR)
ent-
ee,
ent-
5aa
4h
,
4/1 dr
(crude
92%
>99%
1.5
,
,
equiv
We gratefully acknowledge the financial support from the Na-
tional Natural Science Foundation of China (No. 21672235, No.
21871287, and No. 21922114), the Science and Technology Com-
mission of Shanghai Municipality (No. 20JC1417100), the Strategic
Priority Research Program of the Chinese Academy of Sciences (No.
XDB20000000), CAS Key Laboratory of Synthetic Chemistry of
Natural Substances, and Shanghai Institute of Organic Chemistry.
ee
50%, >20/1 dr, >99%
SiMe2Ph
Ph
ee ent-
O
Ph Me
TiCl
equiv)
4 (2
Ph
CH2Cl2 -60 o 24 h
Me
H
Me
9aah
Ph
,
C,
Me
ee,
OH
1H NMR)
ee
ent-
ent-
5aa
,
4h
98%
,
,
8/1 dr
(crude
92%
1.5
equiv
53%, >20/1 dr, >99%
References
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2021
Manuscript revised: XXXX, 2021
Manuscript accepted: XXXX, 2021
Accepted manuscript online: XXXX, 2021
Version of record online: XXXX, 2021
Brown, M. K.; May, T. L.; Baxter, C. A.; Hoveyda, A. H. All-Carbon
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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Entry for the Table of Contents
Asymmetric Synthesis of Chiral 1,3-Disubstituted Allylsilanes with Copper(I)-Catalyzed 1,4-Conjugate Silylation of α,β-Unsaturated Sulfones
Xian-Liang Wang, Xing-Hao Yin, Jun-Zhao Xiao, Xue-Shun Jia, Liang Yin*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
mol
NHC-4-CuCl
%)
R'CHO
LDA
equiv)
equiv)
(5
NaOEt/NaOMe
(1.5
(3.0
PhMe
O
S
2Si
O
S
SiMe2Ph
R'
PhMe2
Si
BT
BT
Bpin
MTBE, -30 o 60 h
C,
THF, rt, 2 h
E/Z >20/1
R
R
R
O
O
=
NHC-4-CuCl
S
N
N
Et
Ph
examples
to 99%
to 96%
31
up
up
N
N
examples
to 75%
12
up
1,3-disubstituted
yield
Ph
CuCl
BT
ee
chiral
Et
yield
allylsilanes
A general method for the asymmetric synthesis of chiral 1,3-disubstituted allylsilanes was developed, including a new copper(I)-NHC com-
plex-catalyzed asymmetric 1,4-conjugate silylation of α,β-unsaturated sulfones and Julia-Kocienski Olefination.
a Department, Institution, Address 1
E-mail:
c Department, Institution, Address 3
E-mail:
b Department, Institution, Address 2
E-mail:
Chin. J. Chem. 2018, template
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim