Nickel-catalyzed enantioselective hydrovinylation of silyl-protected allylic alcohols: An efficient access to homoallylic alcohols with a chiral quaternary center

Article abstract of DOI:10.1007/s11426-010-4036-6

Asymmetric hydrovinylation of silyl-protected allylic alcohols catalyzed by nickel complexes of chiral spiro phosphoramidite ligands was developed. A series of homoallylic alcohols with a chiral quaternary center were produced in high yields (up to 97%) and high enantioselectivities (up to 95% ee). The reaction provides an efficient method for preparing bifunctional compounds with a chiral quaternary carbon center.

Full text of DOI:10.1007/s11426-010-4036-6

SCIENCE CHINA
Chemistry
September 2010 Vol.53 No.9: 1899–1906
doi: 10.1007/s11426-010-4036-6
• ARTICLES •
Nickel-catalyzed enantioselective hydrovinylation of silyl-protected
allylic alcohols: An efficient access to homoallylic alcohols
with a chiral quaternary center
ZHANG Qi, ZHU Shou-Fei, CAI Yan, WANG Li-Xin & ZHOU Qi-Lin*
State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China
Received May 1, 2010; accepted June 1, 2010
Asymmetric hydrovinylation of silyl-protected allylic alcohols catalyzed by nickel complexes of chiral spiro phosphoramidite
ligands was developed. A series of homoallylic alcohols with a chiral quaternary center were produced in high yields (up to
97%) and high enantioselectivities (up to 95% ee). The reaction provides an efficient method for preparing bifunctional com-
pounds with a chiral quaternary carbon center.
asymmetric hydrovinylation, chiral spiro phosphorus ligands, functionalized olefins, chiral quaternary center
pounds. Recently, we have developed nickel-catalyzed hy-
1 Introduction
drovinylation of -ketal vinylarenes for preparing vinyl
aldehydes with high yields and high chemoselectivities [14].
The asymmetric version of this reaction was also attempted
by using chiral spiro phosphorus ligands; however, a very
poor enantioselectivity (24% ee) was obtained. As a part of
our continuous efforts on this subject, here we report the
nickel-catalyzed highly enantioselective hydrovinylation of
silyl-protected allylic alcohols, providing a direct protocol
for the construction of homoallylic alcohols with a chiral
quaternary carbon center.
Transition metal-catalyzed carbon-carbon bond formation
reactions lie at the heart of organic synthesis and have
drawn intensive research attention. Ni-catalyzed asymmetric
hydrovinylation reaction, which uses abundantly available
ethylene as a starting material to construct valuable chiral
compounds, is an atom-economical carbon-carbon bond-
forming reaction and has a high potential for wide applica-
tions in fine chemicals as well as pharmaceutical industry
[1–3]. In the past decades, great efforts have been devoted
to this field and several chiral nickel catalysts have been
developed for highly selective hydrovinylation of unfunc-
tionalized olefins including vinylarenes [4–8], -alkylvi-
nylarenes [9, 10], strained olefins [11], and 1,3-dienes [12,
13]. However, the hydrovinylation of functionalized olefins
remains a challenge.
2 Results and discussion
Initially, the hydrovinylation of tert-butyldimethyl-(2-
phenylallyloxy)silane (1a) was performed in CH2Cl2 at
room temperature using a nickel catalyst generated in situ
from 2 mol% [Ni(allyl)Br]2, 4 mol% (Sa,R,R)-SIPHOS-PE,
and 5 mol% NaBArF (sodium tetrakis[3,5-bis-(trifluoro-
methyl)phenyl]borate). To our delight, the hydrovinylation
product 2a was obtained with good yield (69%) and moder-
ate ee value (41% ee) (Scheme 1). The major competitive
It is of significance that the hydrovinylation of function-
alized olefin provides multi-functionalized products, which
have wide applications in the synthesis of bioactive com-
*Corresponding author (email: qlzhou@nankai.edu.cn)
© Science China Press and Springer-Verlag Berlin Heidelberg 2010
chem.scichina.com
www.springerlink.com

1900
ZHANG Qi, et al. Sci China Chem September (2010) Vol.53 No.9
protecting group was introduced into the allylic alcohol
substrate, the hydrovinylation reaction became applicable.
Smaller silyl group TMS (trimethylsilyl) gave higher yield
and higher enantioselectivity (60% ee) (entry 3); however,
bulkier silyl group TIPS (tri-iso-propylsilyl) led to a low
reactivity and low enantioselectivity (entry 4). Other pro-
tecting groups such as MOM (methoxymethyl) and benzyl
were also examined, and poor enantioselectivities were ob-
tained (entries 5 and 6).
To improve the enantioselectivity of hydrovinylation, the
reaction parameters were carefully optimized. Different
solvents were compared; however, none of the other sol-
vents gave results superior to CH2Cl2 (Table 2, entries 2–5).
Lower temperatures were found to facilitate enantioselectivity
of the reaction. When the reaction temperature was decreased
from room temperature to 0 °C, 40 °C and 60 °C, the
enantioselectivity of the reaction was enhanced continu-
ously from 60% ee to 81% ee (entries 6–8), albeit a longer
reaction time was needed for a full conversion at low tem-
perature. At the same time, the yield of hydrovinylation
products also increased from 56% to 77% (entries 1 and 8).
A number of chiral spiro phosphorus ligands developed
in our laboratory [15] were tested in the hydrovinylation
reaction of 1c (Figure 1). Ligand (Sa,R,R)-SIPHOS-PE was
found to be the best choice of ligands in terms of the yield
and enantioselectivity of the reaction.
A variety of trimethyl(2-arylallyloxy)silanes were inves-
tigated in the hydrovinylation reaction under the optimal
reaction conditions. All substrates with a meta- or para-
substituent on the phenyl ring made the hydrovinylation
reaction proceed smoothly and produce the corresponding
homoallylic alcohols with a chiral quaternary carbon center
in moderate to good yields (42%–97%) and good to high
enantioselectivities (76%–95% ee) (Table 3, entries 1–12).
Scheme 1 The Ni-catalyzed asymmetric hydrovinylation reaction of tert-
butyldimethyl(2-phenylallyloxy)silane. TBDMS is tert-butyldimethylsilyl.
side-reaction was the migration of the double bond in sub-
strate 1a to generate the by-product 3a, which commonly
occurs in hydrovinylation reactions.
In our previous studies, we found that the coordinating
property of the functional group of olefin substrates influ-
ences the reactivity and selectivity of the reaction in nickel-
catalyzed hydrovinylation. A strong coordinating group
occupies one of the coordinating sites of nickel and impedes
the coordination of ethylene to nickel, and consequently
prevents the hydrovinylation reaction. We thus believe that
the choice of right protection of the functional group on
olefin substrate is crucial for obtaining high reactivity,
chemoselectivity, and enantioselectivity in the hydrovinyla-
tion reaction of functionalized olefins. Table 1 shows the
results of hydrovinylation of the allylic alcohol with differ-
ent protecting groups. The reactivity of unprotected allylic
alcohol 1b was very low, and complex products were
obtained in the reaction (Table 1, entry 2). When a silyl-
Table 2 Ni-catalyzed asymmetric hydrovinylation reaction of trimethyl
(2-phenylallyloxy)silane: optimizing reaction conditions a)
Table 1 Ni-catalyzed asymmetric hydrovinylation of allyl alcohol: pro-
tecting groups a)
Entry
Solvent
CH2Cl2
toluene
Et2O
Temp. Time Conv. (%) b) Yield (%) ee (%)
Entry Substrate
PG
TBDMS
H
Yield of 4c (%) b) ee (%) c) of 4c
1
2
3
4
5
6
7
8
rt
rt
rt
rt
rt
< 1 h
3 h
100
39
56
5
60
49

1
2
3
4
5
6
1a
1b
1c
1d
1e
1f
69
ND d)
56
41

3 h
trace
28

TMS
TIPS
MOM
Bn
60
CHCl3
4.5 h
4.5 h
10
trace
59
78
77
53
ND
68
79
81
31
25
CH2ClCH2Cl
CH2Cl2
CH2Cl2
CH2Cl2
29
49
35 e)
22
20 e)
0 °C 15 min
100
99
a) Reaction conditions: [Ni(allyl)Br]2 (0.01 mmol), (Sa,R,R)-SIPHOS-PE
(0.02 mmol), NaBArF (0.024 mmol), substrate (0.5 mmol), CH2Cl2 (2.5 mL),
rt, 1 to 3 h. b) Yield for two steps. c) Determined by SFC (supercritical
fluid chromatography) using a Chiralcel OJ-H column. d) Not determined.
e) Date for deprotecting product 5.
30 min
5 h
40 °C
60 °C
99
a) Reaction conditions and analysis were the same as those in Table 1,
entry 3. b) Determined by GC using a HP-5 column.

ZHANG Qi, et al. Sci China Chem September (2010) Vol.53 No.9
1901
ties (entries 8–11 vs. 3–6). The substrates with 2-biphenyl
(1l) and 3,5-dimethylenedioxyphenyl (1q) also provided
good yields and enantioselectivities (entries 7 and 12). The
ortho substitution on the phenyl ring of the substrate fully
prohibited the reaction under standard conditions (data not
shown). In addition to styrene derivatives, the substrates
containing naphthyl (1r) and thiophenyl (1s) groups could
also undergo the hydrovinylation reaction with high yields
and good enantioselectivities (entries 13 and 14).
The double bond and hydroxyl group present in the
products of asymmetric hydrovinylation provide a potential
for conversion to various chiral bifunctional compounds,
which are significant intermediates in the synthesis of natu-
ral products and pharmaceuticals. For example, oxidation of
compound (S)-4c with ozone and hydrogen perhydroxide
produced (S)--methyltropic acid (6), which is a key inter-
mediate for the synthesis of chiral drug (S)-Atromepine
(Scheme 2) [16].
Figure 1 Ligand screening (reaction conditions were the same as those in
Table 2, entry 8).
Table 3 Asymmetric hydrovinylation of trimethyl(2-arylallyloxy)silanes a)
Entry Substrate
Ar
Product Yield (%) ee (%)
1
2 b)
1c
1g
1h
1i
C6H5
4c
4g
4h
4i
77
91
97
80
69
62
82
86
49
42
49
81 (R)
78 (R)
85
4-MeC6H4
4-MeOC6H4
4-FC6H4
3
4
94
5
1j
4-ClC6H4
4-BrC6H4
4-PhC6H4
3-MeOC6H4
3-FC6H4
4j
92
6
1k
1l
4k
4l
95
Scheme 2 Asymmetric synthesis of (S)--methyltropic acid, an interme-
diate in the synthesis of (S)-Atromepine.
7
80
8
1m
1n
1o
1p
4m
4n
4o
4p
76
9
91
3 Conclusions
10
11
3-ClC6H4
3-BrC6H4
88
85
In conclusion, highly enantioselective nickel-catalyzed asym-
metric hydrovinylation of functionalized olefins, silyl-protected
allylic alcohols, was realized by using chiral spiro phos-
phoramidite ligands. The reaction provides a practically
useful and efficient method for the construction of bifunc-
tional compounds with a chiral quaternary carbon center.
12
13
14
1q
1r
1s
4q
4r
4s
92
92
90
89
81
73
2-naphthyl
a) Reaction conditions and analysis were the same as those in Table 2,
entry 8. The by-products were the enolsilylethers formed by migration of
the double bond in substrates. b) The reaction was performed at 40 °C.
4 Experimental
The substrates 1g and 1h, containing an electron-donating
group at the para-position of phenyl ring, gave higher yields
(91% and 97%) and lower ee values (78% ee and 85% ee)
(entries 2 and 3). While the substrates 1i, 1j and 1k having
an electron-withdrawing group at the para-position of phenyl
ring gave lower yields (62%–80%) but higher ee values
(92%–95% ee) (entries 4–6). The substrates with a meta-
substituent afforded lower yields or lower enantioselectivi-
4.1 General
The reactions and manipulations which are sensitive to
moisture or air were performed in an argon-filled glove box
(VAC DRI-LAB HE 493) or using standard Schlenk tech-
niques. Commercially available reagents were used as re-
ceived without further purification unless otherwise noted.
Ethylene (99.9%) was purchased from BAPB Gases Com-

1902
ZHANG Qi, et al. Sci China Chem September (2010) Vol.53 No.9
pany, Ltd., Beijing. Anhydrous dichloromethane, DCE,
chloroform and DMF were distilled from calcium hydride
under nitrogen before use. Anhydrous toluene, THF and
ether were distilled from sodium benzophenone ketyl under
nitrogen before use. [Ni(allyl)Br]2 [17], NaBArF [18, 19]
and chiral spiro phosphorous ligands [20–22] were prepared
according to the previously reported procedures. Ligands
ShiP, SIPHOS, and SIPHOS-PE are commercially available
from Aldrich or Strem Co. The 2-arylprop-2-en-1-ol was
prepared by reaction of arylmagnesium bromide and prop-
2-yn-1-ol in the presence of a catalytic amount of CuI ac-
MHz, CDCl3)  7.21 (d, J =8.7 Hz, 2H), 6.72 (d, J =8.7 Hz,
2H), 5.21 (s, 1H), 5.13 (s, 1H), 4.33 (s, 2H), 3.66 (s, 3H), 0.00
(s, 9H); 13C NMR (75 MHz, CDCl3)  159.7, 146.6, 131.9,
127.5, 114.1, 110.8, 64.9, 55.5, 0.0; HRMS (EI) Calcd for
C13H20O2Si: 236.1233; Found 236.1237.
(2-(4-Fluorophenyl)allyloxy)trimethylsilane (1i)
1
Colorless oil, 60% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  7.43 (dd, J = 8.8 and 5.6 Hz, 2H), 7.04
(t, J = 8.8 Hz, 2H), 5.43 (s, 1H), 5.42 (s, 1H), 4.53 (s, 2H),
0.22 (s, 9H); 13C NMR (100 MHz, CDCl3)  163.9, 161.4,
146.2, 135.3, 128.0, 127.9, 115.4, 115.2, 112.2, 64.7, 0.3;
HRMS (EI) Calcd for C12H17FOSi: 224.1033; Found
224.1032.
1
cording to the previously reported procedure [23]. H and
13C NMR spectra were recorded on a Varian Mercury Plus
400 spectrometer at 400 MHz (1H NMR) and 100 MHz (13C
NMR) or a Bruker AV 300 spectrometer at 300 MHz (1H
NMR) and 75 MHz (13C NMR) in CDCl3. Chemical shifts
were reported in ppm downfield from internal Me4Si.
HRMS were recorded on a VG ZAB-HS mass spectrometer
with EI resource. GC analyses were performed using a
Hewlett Packard Model HP 6890 Series equipped with
HP-5 column. HPLC analyses were performed on a Waters
2996 chromatography. SFC analyses were performed on
Agilent 1200 Series.
(2-(4-Chlorophenyl)allyloxy)trimethylsilane (1j)
1
Colorless oil, 34% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  7.22–7.13 (m, 4H), 5.28 (s, 1H), 5.23
(s, 1H), 4.32 (s, 2H), 0.00 (s, 9H); 13C NMR (100 MHz,
CDCl3)  146.0, 137.6, 133.7, 128.6, 127.6, 112.9, 64.5,
0.2; HRMS (EI) Calcd for C12H17ClOSi: 240.0737; Found
240.0741.
(2-(4-Bromophenyl)allyloxy)trimethylsilane (1k)
1
4.2 Preparation and analytic data of substrates
Colorless oil, 47% yield (from prop-2-yn-1-ol). H NMR
(400 MHz, CDCl3)  7.45 (d, J = 8.4 Hz, 2H), 7.30 (d, J =
8.4 Hz, 2H), 5.45 (s, 1H), 5.40 (s, 1H), 4.48 (s, 2H), 0.17 (s,
9H); 13C NMR (100 MHz, CDCl3)  146.1, 139.1, 131.6,
128.0, 121.9, 113.0, 64.5, 0.2; HRMS (EI) Calcd for
C12H17BrOSi: 284.0232; Found 284.0235.
Typical procedure for preparation of trimethyl(2-arylallyloxy)
silane: A mixture of 2-arylprop-2-en-1-ol (10 mmol) and
pyridine (11 mmol) in THF (50 mL) was stirred at room
temperature, and TMSCl (10 mmol) was added dropwise.
After stirring for 1 h, the resulting suspension was filtrated.
The filtrate was concentrated under vacuum and the residue
was purified by chromatography (ethyl acetate/petroleum
ether = 1:10, v/v) to give trimethyl(2-arylallyloxy)silane. The
analysis data of trimethyl(2-arylallyloxy)silane are illus-
trated below.
(2-(4-Biphenyl)allyloxy)trimethylsilane (1l)
White solid (mp: 58–60 °C), 41% yield (from prop-2-yn-1-ol).
1H NMR (300 MHz, CDCl3)  7.59–7.30 (m, 9H), 5.52 (s,
1H), 5.44 (s, 1H), 4.56 (s, 2H), 0.20 (s, 9H); 13C NMR (75
MHz, CDCl3)  146.6, 141.0, 140.8, 138.2, 129.1, 127.7,
127.3, 127.2, 126.8, 112.3, 64.7, 0.0; HRMS (EI) Calcd for
C18H22OSi: 282.1440; Found 282.1433.
Trimethyl(2-phenylallyloxy)silane (1c)
1
Colorless oil, 92% yield (from prop-2-yn-1-ol). H NMR
(400 MHz, CDCl3)  7.43–7.26 (m, 5H), 5.45 (s, 1H), 5.39
(s, 1H), 4.52 (s, 2H), 0.17 (s, 9H); 13C NMR (100 MHz,
CDCl3)  147.1, 139.3, 128.6, 127.9, 126.3, 112.1, 64.6, 0.2;
HRMS (EI) Calcd for C12H18OSi: 206.1127; Found 206.1144.
(2-(3-Methoxyphenyl)allyloxy)trimethylsilane (1m)
1
Colorless oil, 34% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  7.35–6.90 (m, 4H), 5.55 (s, 1H), 5.50
(s, 1H), 4.60 (s, 2H), 3.86 (s, 3H), 0.28 (s, 9H); 13C NMR
(75 MHz, CDCl3)  160.1, 147.3, 141.1, 129.7, 119.0, 113.4,
112.6, 112.5, 64.8, 55.5, 0.0; HRMS (EI) Calcd for
C13H20O2Si: 236.1233; Found 236.1234.
Trimethyl(2-p-tolylallyloxy)silane (1g)
1
Colorless oil, 68% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  7.16 (d, J = 8.1 Hz, 2H), 6.99 (d, J =
7.5 Hz, 2H), 5.25 (s, 1H), 5.18 (s, 1H), 4.34 (s, 2H), 2.19 (s,
3H), 0.00 (s, 9H); 13C NMR (100 MHz, CDCl3)  146.9,
137.6, 136.4, 129.3, 126.2, 111.3, 64.6, 21.4, 0.1; HRMS
(EI) Calcd for C13H20OSi: 220.1283; Found 220.1284.
(2-(3-Fluorophenyl)allyloxy)trimethylsilane (1n)
1
Colorless oil, 56% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  7.12–6.75 (m, 4H), 5.29 (s, 1H), 5.25
(s, 1H), 4.31 (s, 2H), 0.00 (s, 9H); 13C NMR (75 MHz,
CDCl3)  165.1, 161.8, 146.4, 142.0, 141.9, 130.3, 130.2,
122.2, 115.1, 114.8, 113.7, 113.5, 64.7, 0.0; HRMS (EI)
(2-(4-Methoxyphenyl)allyloxy)trimethylsilane (1h)
Colorless oil, 29% yield (from prop-2-yn-1-ol). 1H NMR (300

ZHANG Qi, et al. Sci China Chem September (2010) Vol.53 No.9
1903
Calcd for C12H17FOSi: 224.1033; Found 224.1034.
7.42–7.26 (m, 5H), 5.43 (d, J = 1.6 Hz, 1H), 5.41 (d, J=2.0
Hz, 1H), 4.54 (s, 2H), 0.95 (s, 9H), 0.12 (s, 6H); 13C NMR
(75 MHz, CDCl3)  147.2, 139.3, 128.4, 127.8, 126.2, 111.5,
64.9, 26.1, 18.5, 0.0; HRMS (EI) Calcd for C11H15OSi
(MC4H9): 191.0892; Found 191.0897.
(2-(3-Chlorophenyl)allyloxy)trimethylsilane (1o)
1
Colorless oil, 49% yield (from prop-2-yn-1-ol). H NMR
(400 MHz, CDCl3)  7.41–7.26 (m, 4H), 5.47 (s, 1H), 5.42
(s, 1H), 4.78 (s, 2H), 0.17 (s, 9H); 13C NMR (75 MHz,
CDCl3)  146.2, 141.4, 134.7, 130.0, 128.1, 126.7, 124.7,
113.6, 64.7, 0.0; HRMS (EI) Calcd for C12H17ClOSi:
240.0737; Found 240.0738.
Triisopropyl(2-phenylallyloxy)silane (1d)
Compound 1d was prepared from 2-phenylprop-2-en-1-ol
and TIPSCl by the same procedure as that for 1a. Pale yel-
1
low oil, 98% yield. H NMR (400 MHz, CDCl3)  7.40–7.28
(2-(3-Bromophenyl)allyloxy)trimethylsilane (1p)
(m, 5H), 5.49 (s, 1H), 5.44 (s, 1H), 4.61 (s, 2H), 1.20–1.09
(m, 21H); 13C NMR (75 MHz, CDCl3)  147.1, 139.3, 128.4,
127.7, 126.0, 111.1, 64.9, 18.2, 12.2; HRMS (EI) Calcd for
C15H23OSi (MC3H7): 247.1518; Found 247.1513.
1
Colorless oil, 33% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  7.40–6.99 (m, 4H), 5.28 (s, 1H), 5.24
(s, 1H), 4.30 (s, 2H), 0.00 (s, 9H); 13C NMR (75 MHz,
CDCl3)  146.1, 141.6, 131.0, 130.2, 129.6, 125.1, 123.0,
113.7, 64.6, 0.0; HRMS (EI) Calcd for C12H17BrOSi:
284.0232; Found 284.0234.
1-(1-(Methoxymethoxy)prop-2-en-2-yl)benzene (1e)
Under nitrogen atmosphere, 2-phenylprop-2-en-1-ol (1.9 g,
14 mmol) was added to the suspension of NaH (0.36 g, 15
mmol) in dry THF (50 mL). After stirring for 4 h at room
temperature, the system turned to brown. The MeOCH2Cl
(1.4 g, 17 mmol) was added dropwise. After stirring over-
night, the resulting suspension was poured to 100 mL water
and extracted with ether three times. The organic layer was
washed by brine and dried over anhydrous Na2SO4. After
filtration and concentration under vacuum, the residue was
purified by chromatography (ethyl acetate/petroleum ether=
1:10, v/v) to give 1-(1-(methoxymethoxy)prop-2-en-2-yl)-
(2-(Benzo[d][1,3]dioxol-5-yl)allyloxy)trimethylsilane (1q)
1
Colorless oil, 32% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  6.78–6.57 (m, 3H), 5.74 (s, 2H), 5.18
(s, 1H), 5.13 (s, 1H), 4.28 (s, 2H), 0.00 (s, 9H); 13C NMR
(75 MHz, CDCl3)  148.1, 147.6, 146.7, 133.7, 119.9, 111.5,
108.4, 107.1, 101.4, 65.0, 0.0; HRMS (EI) Calcd for
C13H18O3Si: 250.1025; Found 250.1058.
Trimethyl(2-(naphthalen-2-yl)allyloxy)silane (1r)
1
Yellow oil, 74% yield (from prop-2-yn-1-ol). 1H NMR (300
MHz, CDCl3)  7.83–7.39 (m, 7H), 5.61 (s, 1H), 5.51 (s,
1H), 4.64 (s, 2H), 0.20 (s, 9H); 13C NMR (75 MHz, CDCl3)
 146.9, 136.5, 133.7, 133.3, 128.5, 128.2, 127.9, 126.5,
126.2, 124.9, 124.8, 112.9, 64.8, 0.0; HRMS (EI) Calcd for
C16H20OSi: 256.1283; Found 256.1290.
benzene (2.1 g, 85% yield) as colorless oil. H NMR (400
MHz, CDCl3)  7.47 (d, J = 6.8 Hz, 2H), 7.36–7.29 (m, 3H),
5.54 (s, 1H), 5.37 (s, 1H), 4.70 (s, 2H), 4.47 (s, 2H), 3.38 (s,
3H); 13C NMR (CDCl3, 75 MHz)  144.2, 138.9, 128.4,
127.8, 126.1, 114.3, 95.5, 68.9, 55.3; HRMS (EI) Calcd for
C11H14O2: 178.0994; Found 178.0995.
1-((2-Phenylallyloxy)methyl)benzene (1f)[24]
Trimethyl(2-(thiophen-2-yl)allyloxy)silane (1s)
1
Compound 1f was prepared from 2-phenylprop-2-en-1-ol,
NaH and BnCl by the similar procedure as that for 1e. Col-
orless oil, 85% yield. 1H NMR (400 MHz, CDCl3)  7.47 (d,
J = 8.0 Hz, 2H), 7.36–7.29 (m, 8H), 5.56 (s, 1H), 5.38 (s,
1H), 4.57 (s, 2H), 4.42 (s, 2H).
Colorless oil, 32% yield (from prop-2-yn-1-ol). H NMR
(300 MHz, CDCl3)  7.04–6.84 (m, 3H), 5.39 (s, 1H), 5.18
(s, 1H), 4.37 (s, 2H), 0.08 (s, 9H); 13C NMR (75 MHz,
CDCl3)  142.7, 141.0, 127.6, 124.6, 123.6, 111.0, 64.7, 0.0;
HRMS (EI) Calcd for C10H16OSSi: 212.0691; Found 212.0697.
tert-Butyldimethyl(2-phenylallyloxy)silane (1a)
4.3 General procedure for asymmetric Ni-catalyzed
hydrovinylation
The mixture of 2-phenylprop-2-en-1-ol (2.4 g, 18 mmol)
and imidazole (13.6 g, 203 mmol) in dry DMF (40 mL) was
stirred at room temperature, and TBDMSCl (3.0 g, 20 mmol)
was added dropwise. After stirring for 20 h, the resulting
solution was poured to 200 mL water and extracted with
CH2Cl2 three times. The organic layer was washed by cold
hydrochloric acid (1 M), saturated NaHCO3 solution and
brine. After dried over anhydrous Na2SO4, the solution was
concentrated under vacuum and the residue was purified by
chromatography (ethyl acetate/petroleum ether = 1:10, v/v)
to give tert-butyldimethyl(2-phenylallyloxy)silane (4.2 g,
95% yield) as colorless oil. 1H NMR (400 MHz, CDCl3) 
Under nitrogen atmosphere, [Ni(allyl)Br]2 (10 mol), chiral
phosphorus ligand (20 mol) and distilled CH2Cl2 (2.5 mL)
were introduced into a Schlenk tube equipped with a stirring
bar. The mixture was stirred at room temperature for 1 min
and transferred to another Schlenk tube containing NaBArF
(24 mol). The resulting mixture was stirred for 3 min at
room temperature and then cooled to the desired tempera-
ture. The inert atmosphere in the Schlenk tube was replaced
by ethylene three times and the trimethyl-(2-arylallyloxy)
silane (0.5 mmol) was introduced. The reaction mixture was

1904
ZHANG Qi, et al. Sci China Chem September (2010) Vol.53 No.9
stirred for specified time (monitored by GC). After the reac-
tion was completed, the mixture was concentrated under
reduced pressure. The residue was resolved by THF (5 mL),
and TBAF (50 mg) was added to the solution. The mixture
was stirred at room temperature until the deprotecting reac-
tion finished. Finally, the resulting mixture was chroma-
tographed on silica gel column to give the pure product. The
analysis data of the products are illustrated below.
J = 18.0 Hz, 1H), 3.67 (s, 2H), 1.45 (s, 1H), 1.32 (s, 3H);
13C NMR (75 MHz, CDCl3)  163.1, 159.9, 143.5, 140.3,
140.2, 128.6, 128.5, 115.2, 115.0, 114.7, 70.0, 46.5, 22.8;
HRMS (EI) Calcd for C11H13FO: 180.0950; Found
180.0950.
2-(4-Chlorophenyl)-2-methylbut-3-en-1-ol (4j)
Colorless oil, 69% yield, 92% ee, []D20 = 20.6 (c 0.65,
ethanol). HPLC condition: Chiralcel OJ-H column, n-hexane/i-
propanol = 97:3, flow rate = 0.8 mL/min, wavelength = 220
nm, tR = 23.32 min for major isomer, tR = 24.79 min for the
minor isomer. 1H NMR (400 MHz, CDCl3)  7.29 (d, J=1.6
Hz, 4H), 6.03 (dd, J = 17.6 and 10.8 Hz, 1H), 5.28 (d, J =
10.8 Hz, 1H), 5.14 (d, J=17.6 Hz, 1H), 3.76 (s, 2H), 1.43 (s,
1H), 1.40 (s, 3H); 13C NMR (75 MHz, CDCl3)  143.1,
132.4, 128.5, 128.4, 115.1, 69.8, 46.7, 22.7; HRMS (EI)
Calcd for C11H13ClO: 196.0655; Found 196.0654.
(2R)-2-Methyl-2-phenylbut-3-en-1-ol (4c) [25]
Colorless oil, 77% yield, 81% ee, []D20 = 18.1 (c 1.9,
ethanol). The absolute configuration of 4c was determined
to be R (see S compound 6). SFC condition: Chiralcel OJ-H
column, sc CO2/i-PrOH = 90:10, flow rate = 2.0 mL/min,
wavelength = 220 nm, pressure =100 bar, tR =5.19 min for S
1
enantiomer, tR = 5.58 min for R enantiomer. H NMR (300
MHz, CDCl3)  7.35–7.30 (m, 4H), 7.25–7.21 (m, 1H), 6.07
(dd, J=17.7 and 11.1 Hz, 1H), 5.26 (dd, J=10.8 and 1.2 Hz,
1H), 5.15 (dd, J = 17.7 and 1.2 Hz, 1H), 3.78 (d, J=3.6 Hz,
2H), 1.46 (s, 1H), 1.42 (s, 3H).
2-(4-Bromophenyl)-2-methylbut-3-en-1-ol (4k)
Colorless oil, 62% yield, 95% ee, []D20 = 20.1 (c 1.0, etha-
nol). HPLC condition: Chiralcel OJ-H column, n-hexane/i-
propanol = 98:2, flow rate = 0.7 mL/min, wavelength = 220
nm, tR = 25.97 min for the major isomer, tR = 27.59 min for
(2R)-2-Methyl-2-p-tolylbut-3-en-1-ol (4g) [26]
Colorless oil, 91% yield, 78% ee, []D20 = 10.4 (c 1.25,
CHCl3). The absolute configuration of 4g was determined to
be R by comparison of the [] value of 4g with reported
data; R-enriched 4g (uncertain ee value): []D20 =2.4 (c 1.2,
CHCl3) [26]. SFC condition: Chiralcel OJ-H column, sc
CO2/i-PrOH = 90:10, flow rate = 2.0 mL/min, wavelength =
220 nm, pressure = 100 bar, tR = 4.89 min for S isomer, tR =
1
the minor isomer. H NMR (400 MHz, CDCl3)  7.44 (d,
J = 8.4 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H), 6.01 (dd, J = 18.0
and 10.8 Hz, 1H), 5.26 (d, J=10.8 Hz, 1H), 5.12 (d, J=17.6
Hz, 1H), 3.74 (s, 2H), 1.45 (s, 1H), 1.38 (s, 3H); 13C NMR
(100 MHz, CDCl3)  143.9, 143.3, 131.7, 129.1, 120.7,
115.3, 70.0, 47.0, 22.9; HRMS (EI) Calcd for C11H13BrO:
240.0150; Found 240.0150.
1
5.48 min for R isomer. H NMR (300 MHz, CDCl3)  7.24
(d, J = 8.1 Hz, 2H), 7.15 (d, J = 8.1 Hz, 2H), 6.07 (dd, J =
17.7 and 10.8 Hz, 1H), 5.25 (dd, J = 10.8 and 0.9 Hz, 1H),
5.14 (dd, J = 17.7 and 0.9 Hz, 1H), 3.77 (d, J=5.7 Hz, 2H),
2.33 (s, 3H), 1.55 (s, 1H), 1.41 (s, 3H).
2-(4-Biphenyl)-2-methylbut-3-en-1-ol (4l)
White solid (mp: 43–45 °C), 82% yield, 80% ee, []D20
=
26.6 (c 1.35, ethanol). SFC condition: Chiralcel OD-H
column, sc CO2/i-PrOH = 80:20, flow rate = 2.0 mL/min,
wavelength=254 nm, pressure=100 bar, tR =7.19 min for the
2-(4-Methoxyphenyl)-2-methylbut-3-en-1-ol (4h) [27]
Colorless oil, 97% yield, 85% ee, []D20 = 21.0 (c 1.5, etha-
nol). SFC condition: Chiralcel OJ-H column, sc CO2/i-
PrOH=90:10, flow rate =2.0 mL/min, wavelength=220 nm,
pressure = 100 bar, tR = 6.56 min for the minor isomer, tR =
7.08 min for the major isomer. 1H NMR (300 MHz, CDCl3)
 7.26 (d, J = 12.0 Hz, 2H), 6.87 (d, J = 11.7 Hz, 2H), 6.05
(dd, J=17.7 and 10.8 Hz, 1H), 5.23 (dd, J=10.8 and 1.2 Hz,
1H), 5.12 (dd, J=17.7 and 1.2 Hz, 1H), 3.79 (s, 3H), 3.74 (s,
2H), 1.45 (s, 1H), 1.40 (s, 3H).
1
major isomer, tR = 8.02 min for the minor isomer. H NMR
(400 MHz, CDCl3)  7.59–7.33 (m, 9H), 6.11 (dd, J = 17.6
and 10.8 Hz, 1H), 5.31 (d, J=10.8 Hz, 1H), 5.20 (d, J=17.6
Hz, 1H), 3.84 (d, J = 6.4 Hz, 2H), 1.57 (s, 1H), 1.47 (s, 3H);
13C NMR (75 MHz, CDCl3)  143.7, 143.6, 140.8, 139.4,
128.9, 127.4, 127.3, 127.2, 127.1, 114.7, 70.1, 46.8, 22.7;
HRMS (EI) Calcd for C17H18O: 238.1358; Found 238.1358.
2-(3-Methoxyphenyl)-2-methylbut-3-en-1-ol (4m)
Colorless oil, 86% yield, 76% ee, []D20 = 17.2 (c 2.25,
ethanol). HPLC condition: Chiralcel OJ-H column, n-hexane/i-
propanol = 90:10, flow rate = 0.8 mL/min, wavelength =220
nm, tR = 19.57 min for the minor isomer, tR = 21.20 min for
the major isomer. 1H NMR (300 MHz, CDCl3)  7.18 (t, J=
7.8 Hz, 1H), 6.87–6.68 (m, 3H), 5.98 (dd, J = 17.4 and 10.8
Hz, 1H), 5.17 (d, J = 10.8 Hz, 1H), 5.07 (d, J=17.4 Hz, 1H),
3.72 (s, 3H), 3.68 (s, 2H), 1.43 (s, 1H), 1.33 (s, 3H); 13C
NMR (100 MHz, CDCl3)  159.9, 146.5, 143.7, 129.6,
2-(4-Fluorophenyl)-2-methylbut-3-en-1-ol (4i)
Colorless oil, 80% yield, 94% ee, []D20 = 16.7 (c 1.6, etha-
nol). HPLC condition: Chiralcel OJ-H column, n-hexane/i-
propanol = 95:5, flow rate = 0.8 mL/min, wavelength = 220
nm, tR = 22.22 min for the major isomer, tR = 24.17 min for
the minor isomer. 1H NMR (300 MHz, CDCl3)  7.23 (dd, J
= 8.7 and 5.4 Hz, 2H), 6.93 (t, J = 8.4 Hz, 2H), 5.95 (dd, J=
17.7 and 11.1 Hz, 1H), 5.18 (d, J = 10.5 Hz, 1H), 5.04 (d,

ZHANG Qi, et al. Sci China Chem September (2010) Vol.53 No.9
1905
119.4, 114.7, 113.8, 111.5, 70.2, 55.4, 47.2, 22.8; HRMS
C12H14O3: 206.0943; Found 206.0945.
(EI) Calcd for C12H16O2: 192.1150; Found 192.1150.
2-Methyl-2-(naphthalen-2-yl)but-3-en-1-ol (4r)
Offwhite solid (mp: 40–42 °C), 92% yield, 81% ee, []D20 =
2-(3-Fluorophenyl)-2-methylbut-3-en-1-ol (4n)
Colorless oil, 49% yield, 91% ee, []D20 = 17.5 (c 0.85,
ethanol). SFC condition: Chiralpak AD-H column, sc CO2/i-
PrOH = 95:5, flow rate = 2.0 mL/min, wavelength =220 nm,
pressure = 100 bar, tR = 7.55 min for the minor isomer, tR =
8.54 min for the major isomer. 1H NMR (300 MHz, CDCl3)
 7.27–7.19 (m, 1H), 7.07–6.97 (m, 2H), 6.86 (t, J=8.1 Hz
1H), 5.97 (dd, J = 17.7 and 10.8 Hz, 1H), 5.21 (d, J = 10.8
Hz, 1H), 5.08 (d, J=17.7 Hz, 1H), 3.70 (s, 2H), 1.34 (s, 3H),
1.32 (s, 1H); 13C NMR (75 MHz, CDCl3)  164.6, 161.3,
143.0, 129.9, 129.7, 122.5, 115.1, 114.4, 114.1, 113.5,
113.2, 69.8, 47.0, 22.6; HRMS (EI) Calcd for C11H13FO:
180.0950; Found 180.0955.
29.0 (c 1.0, ethanol). ee value of 4r was determined by
converting the alcohol to the corresponding benzoate and
analyzing the ester on chiral HPLC. HPLC condition: Chiralcel
OJ column, n-hexane/i-propanol = 90:10, flow rate = 0.8
mL/min, wavelength = 254 nm, tR = 12.73 min for the minor
1
isomer, tR = 28.63 min for the major isomer. H NMR (300
MHz, CDCl3)  7.68–7.65 (m, 4H), 7.35–7.31 (m, 3H), 6.00
(dd, J = 17.7 and 10.8 Hz, 1H), 5.16 (d, J = 10.8 Hz, 1H),
5.03 (d, J = 17.7 Hz, 1H), 3.70 (s, 2H), 1.55 (s, 1H), 1.37 (s,
3H); 13C NMR (75 MHz, CDCl3)  143.7, 142.0, 133.5,
132.2, 128.1, 127.5, 126.1, 125.9, 125.7 125.5, 114.9, 69.9,
47.2, 22.8; HRMS (EI) Calcd for C15H16O: 212.1201;
Found 212.1206.
2-(3-Chlorophenyl)-2-methylbut-3-en-1-ol (4o)
Colorless oil, 42% yield, 88% ee, []D20 = 15.7 (c 0.75,
ethanol). SFC condition: Chiralpak AD-H column, sc CO2/i-
PrOH = 95:5, flow rate = 2.0 mL/min, wavelength =220 nm,
pressure = 100 bar, tR = 11.32 min for the minor isomer, tR =
12.27 min for the major isomer. 1H NMR (400 MHz, CDCl3)
 7.33–7.22 (m, 4H), 6.03 (dd, J = 17.6 and 10.8 Hz, 1H),
5.29 (d, J = 10.8 Hz, 1H), 5.16 (d, J = 17.6 Hz, 1H), 3.77 (s,
2H), 1.48 (s, 1H), 1.41 (s, 3H); 13C NMR (75 MHz, CDCl3)
 146.9, 142.9, 134.4, 129.6, 127.4, 126.7, 125.2, 125.1,
115.2, 69.8, 47.0, 22.6; HRMS (EI) Calcd for C11H13ClO:
196.0655; Found 196.0654.
2-methyl-2-(thiophen-2-yl)but-3-en-1-ol (4s)
Colorless oil, 90% yield, 73% ee, []D20 = 26.6 (c 1.7,
ethanol). SFC condition: Chiralcel OJ-H column, sc CO2/i-
PrOH = 95:5, flow rate = 2.0 mL/min, wavelength =220 nm,
pressure = 100 bar, tR = 23.11 min for the minor isomer, tR =
24.20 min for the major isomer. 1H NMR (300 MHz, CDCl3)
 7.11 (d, J = 4.8 Hz, 1H), 6.90–6.81 (m, 2H), 6.01 (dd, J=
17.4 and 10.8 Hz, 1H), 5.14 (d, J = 10.8 Hz, 1H), 5.07 (d,
J = 17.4 Hz, 1H), 3.61 (s, 2H), 1.79 (s, 1H), 1.41 (s, 3H);
13C NMR (75 MHz, CDCl3)  149.5, 142.9, 126.8, 124.0,
114.7, 71.1, 45.9, 23.5; HRMS (EI) Calcd for C9H12OS:
168.0609; Found 168.0604.
2-(3-Bromophenyl)-2-methylbut-3-en-1-ol (4p)
Colorless oil, 49% yield, 85% ee, []D20 = 14.0 (c 1.85,
ethanol) SFC condition: Chiralpak AD-H column, sc CO2/i-
PrOH = 95:5, flow rate = 1.0 mL/min, wavelength =220 nm,
pressure = 100 bar, tR = 30.64 min for the minor isomer, tR =
32.77 min for the major isomer. 1H NMR (400 MHz, CDCl3)
 7.49–7.19 (m, 4H), 6.02 (dd, J = 17.6 and 10.8 Hz, 1H),
5.29 (dd, J = 10.8 and 0.8 Hz, 1H), 5.16 (dd, J=17.6 and 0.8
Hz, 1H), 3.76 (d, J = 5.2 Hz, 2H), 1.47 (s, 1H), 1.40 (s, 3H);
13C NMR (75 MHz, CDCl3)  147.1, 142.9, 130.3, 130.0,
129.7, 125.6, 122.7, 115.3, 69.8, 47.0, 22.6; HRMS (EI)
Calcd for C11H13BrO: 240.0150; Found 240.0150.
4.4 Preparation of (S)--methyltropic acid (6) [16]
(S)--Methyltropic acid was synthesized by the same
method as that used in the previous paper [14]. Yield: 77%,
dark brown oil. []D20 = 19.0 (c 1.0, CHCl3) ([]D25 = 19.4
(c 1.65, CHCl3) for S-enriched 6) [28]; 1H NMR (400 MHz,
CDCl3)  7.35–7.30 (m, 5H), 4.10 (d, J= 11.6 Hz, 1H), 3.65
(d, J = 11.2 Hz, 1H), 1.68 (s, 3H).
We thank the National Natural Science Foundation of China, the National
Basic Research Program of China (973 Program) (2006CB806106,
2010CB833300), the Ministry of Health (2009ZX09501-017), and “111”
Project of the Ministry of Education of China (B06005) for financial support.
2-(Benzo[d][1,3]dioxol-5-yl)-2-methylbut-3-en-1-ol (4q)
Colorless oil, 92% yield, 89% ee, []D20 =22.0 (c 0.5, etha-
nol). HPLC condition: Chiralcel OJ-H column, n-hexane/
i-propanol = 90:10, flow rate = 0.8 mL/min, wavelength =
220 nm, tR = 21.64 min for the minor isomer, tR =22.88 min
for the major isomer. 1H NMR (300 MHz, CDCl3) 
6.77–6.66 (m, 3H), 5.93 (dd, J = 17.7 and 10.8 Hz, 1H),
5.83 (s, 2H), 5.14 (d, J = 10.8 Hz, 1H), 5.03 (d, J=17.7 Hz,
1H), 3.62 (s, 2H), 1.61 (s, 1H), 1.28 (s, 3H); 13C NMR (75
MHz, CDCl3)  147.8, 146.0, 143.7, 138.5, 120.0, 114.3,
108.0, 107.8, 101.0, 70.1, 46.7, 22.9; HRMS (EI) Calcd for
1
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