Organocatalytic Enantioselective Allylic Etherification of Morita-Baylis-Hillman Carbonates and Silanols

Article abstract of DOI:10.1021/acs.joc.6b01931

The organocatalytic asymmetric allylic etherification reaction of Morita-Baylis-Hillman carbonates and silanols was reported for the first time. With modified cinchona alkaloid (DHQD)₂PYR as the catalyst, a series of aromatic, heterocyclic, or aliphatic Morita-Baylis-Hillman carbonates (25 examples) worked well with triphenylsilanol, affording the corresponding products in moderate to good yields (up to 98%), high regioselectivities (>20:1), and good enantioselectivities (up to 92%). When dimethylphenylsilanol was used as the nucleophile, the product was obtained in 60% yield and 87% ee.

Full text of DOI:10.1021/acs.joc.6b01931

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Note
Organocatalytic Enantioselective Allylic Etherification
of Morita-Baylis-Hillman Carbonates and Silanols
Hui-Li Liu, Ming-Sheng Xie, Gui-Rong Qu, and Hai-Ming Guo
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01931 • Publication Date (Web): 22 Sep 2016
Downloaded from http://pubs.acs.org on September 23, 2016
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Organocatalytic Enantioselective Allylic Etherification of
Morita-Baylis-Hillman Carbonates and Silanols
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HuiꢀLi Liu, MingꢀSheng Xie*, GuiꢀRong Qu, HaiꢀMing Guo*
Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Collaborative
Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of
Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China
ABSTRACT
The organocatalytic asymmetric allylic etherification reaction of MoritaꢀBaylisꢀHillman
carbonates and silanols was reported for the first time. With modified cinchona alkaloid
(
DHQD)
2
PYR as the catalyst,
a
series of aromatic, heterocyclic or aliphatic
MoritaꢀBaylisꢀHillman carbonates (25 examples) worked well with triphenylsilanol, affording the
corresponding products in moderate to good yields (up to 98%), high regioselectivities (>20:1)
and good enantioselectivities (up to 92%). When dimethylphenylsilanol was used as the
nucleophile, the product was obtained in 60% yield and 87% ee.
1
The asymmetric nucleophilic substitution reactions of allylic substrates and various nucleophiles
2
ꢀ13
(
such as C, N, O, P, S, B)
are powerful methods to construct carbonꢀcarbon and
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carbonꢀheteroatom bonds. Among them, allylic substitutions with Oꢀnucleophiles have received
considerable attention, and many outstanding studies in asymmetric allylic etherification (AAE)
7
8
have been reported, in which allylic substitutions reacted with phenols , benzyl alcohols , aliphatic
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alcohols , alkoxides and carboxylates are general strategies to synthesize of optically pure
allylic ethers. In 2009, Chen’s group reported the enantioselective Oꢀallylic alkylation of MBH
12
carbonates using acetophenone oxime as the O nucleophile. Later, Jiang’s group achieved allylic
1
3
hydroxylation of MBH carbonates which using H
2
O as the nucleophile directly. By contrast,
silicon nucleophiles, such as silane and silanol, have been less studied in the asymmetric allylic
14
substitution reactions. In 2008, Carreira’s group used silanolates as the water surrogates to give
15
chiral allylic alcohols conveniently. It was worth mentioning that Hartwig’s group first reported
one example of an asymmetric allylic substitution reaction of cinnamyl acetate catalyzed by chiral
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Ir complex (Scheme 1a). Later Xu’s and Moberg’s groups used triphenylsilanol and
1,3ꢀdiarylꢀ2ꢀpropenyl acetate to form chiral allylic etherification products catalyzed by chiral Pd
complex with N,P and O,P ligands, respectively (Scheme 1b). Considering that there is scarce
report using triphenylsilanol as the nucleophile and no report about allylic substitution reaction of
MoritaꢀBaylisꢀHillman (MBH) carbonates and silanol, we will report silanol as the nucleophile to
N N
react with MBH carbonates through successive S 2'ꢀS 2' reaction under chiral organocatalysts to
form chiral allylic etherification products (Scheme 1c).
a) Hartwig’s work
b) Xu’s work and Moberg’s work
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c) This work
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Scheme 1. Asymmetric allylic substitution reactions with silanol as the nucleophile
Scheme 2. Preliminary experiments
Initially, Ph SiH 1a was used as the nucleophile to react with MBH carbonate 2a in the
presence of DABCO, NaH and H O at room temperature, giving the etherification product 4a in
3
2
4
0% yield (Scheme 2). The structure of etherification product 4a was confirmed by Xꢀray
diffraction. This unexpected result made us think where the oxygen came from, so we performed a
series of control experiments (see supporting information for details), and found that Ph SiH could
3
be transformed into Ph
3
2
SiOH 3a in the presence of DABCO, NaH and H O (which is the oxygen
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source) at room temperature, which was a new way to get Ph SiOH from Ph SiH. Then Ph SiOH
3
3
3
3a reacted with MBH carbonate 2a to give the product 4a in the presence of DABCO.
a
Table 1. Optimization of the reaction conditions
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yield 7aa/
ee
(%)
56
8
entry cat 5a:3a
base
solvent
b
c
d
(
%)
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8aa
t
1
2
3
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5
6
7
8
9
6a 1:2.5 NaO Bu MTBE
4:1
t
6b 1:2.5 NaO Bu MTBE
15:1
8:1
t
6c 1:2.5 NaO Bu MTBE
83
82
87
t
6d 1:2.5 NaO Bu MTBE
12:1
t
6e 1:2.5 NaO Bu MTBE
12:1
t
6f
1:2.5 NaO Bu MTBE
10:1
ꢀ67
87
54
89
89
89
89
86
89
89
87
90
92
90
6e 1:2.5 Cs
2
CO
3
MTBE
MTBE
10:1
6e 1:2.5
6e 1:2.5
3
Et N
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
i
i
i
i
i
i
i
i
i
i
i
Pr
2
2
2
2
2
2
2
2
2
2
2
EtN MTBE
EtN MTBE
EtN MTBE
EtN MTBE
1
0
6e
6e 1.5:1
6e
2:1
1:1
Pr
Pr
Pr
Pr
Pr
Pr
Pr
Pr
Pr
Pr
11
12
1
1
1
3
4
5
6e 1.5:1
6e 1.5:1
6e 1.5:1
6e 1.5:1
6e 1.5:1
6e 1.5:1
6e 1.5:1
EtN
EtN
THF
EE
EtN anisole
EtN DCM
16
e
1
7
EtN MTBE
EtN MTBE
EtN MTBE
f
1
8
g
1
9
a
Unless otherwise noted, the reaction conditions were: 5a (0.05 mmol) and 3a (2.5 equiv) in
o
b
c
1
solvent (0.5 mL) at 100 C for 10 h. Isolated yield. Determined by the H NMR spectra of the
d
e
o
f
o
crude products. The ee of 7aa was determined by chiral HPLC analysis. 90 C for 12 h. 70 C
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g
for 48 h. 5 mol % catalyst loading.
Subsequently, MBH carbonate (5a) and Ph
3
SiOH (3a) were chosen as the model substrates and
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t
o
NaO Bu was used as the base in tertꢀbutyl methyl ether (MTBE) at 100 C. When quinidine (6a)
was used as the catalyst, the products 7aa and 8aa were formed in 36% total yield and 56% ee,
with poor regioselectivity in which the branch product 7aa was the major form (Table 1, entry 1).
When quinineꢀderived thiourea catalyst 6b was used as the catalyst, the desired product was only
2
obtained in 14% yield and 8% ee (Table 1, entry 2). When C ꢀsymmetric (bis)cinchona alkaloid
2 2 2
derivatives such as (DHQD) PHAL (6c), (DHQD) AQN (6d), (DHQD) PYR (6e) and
(
2
DHQ) PYR (6f) were used, the ee values were improved significantly (Table 1, entries 3ꢀ6), in
which (DHQD) PYR gave the corresponding product in 52% yield, 12:1 regioselectivity and 87%
2
i
ee (Table 1, entry 5). Other bases including Cs
2
CO
3
, Et
3
N, and Pr
2
EtN were tested (Table 1, entry
i
7ꢀ9), and found that Pr
2
EtN was the best base affording the desired product in 80% yield, high
regioselectivity (>20:1) and 89% ee (Table 1, entry 9). To further increase the yield, the substrate
ratio of the 5a and 3a was examined (Table 1, entries 9ꢀ12). The better ratio of 5a:3a was 1.5:1,
giving the etherification product in 88% yield, high regioselectivity (>20:1) and 89% ee (Table 1,
entry 11). Switching the reaction solvent from MTBE to THF, EE, anisole or DCM proved that
MTBE was the best reaction medium for this reaction (Table 1, entries 12 vs 13ꢀ16). When the
o
reaction was performed at a lower temperature 90 C, the ee value of 7aa was improved to 90%
and the yield increased from 88% to 91% (Table 1, entry 17 vs 11). By lowering the reaction
o
temperature to 70 C after 48 h, the ee value of 7aa was improved to 92% along with sharply
decreased in the yield (Table 1, entry 18). Lowering the catalyst loading from 10 mol % to 5
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mol %, the ee value could be maintained, along with lower yield (Table 1, entry 19). Therefore,
the optimal reaction conditions were found to be (DHQD)
2
PYR (6e) (10 mol %) as the catalyst,
i
o
Pr
2
EtN as the base in MTBE at 90 C for 12 h.
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a
Scheme 3. Substrate scope of asymmetric allylic etherification of MBH carbonates and silanols
a
i
2 2
Reaction condition: 3a (0.05 mmol), 5aꢀ5y (1.5 equiv), Pr EtN (1.0 equiv), (DHQD) PYR (10
o
mol %), and MTBE (0.4 mL) in a sealed pressure tube at 90 C. Isolated yields are reported with
b
high regioselectivities (>20:1). The ee values were determined by chiral HPLC analysis.
Measured after desilylation to the corresponding alcohol 9.
With the optimal conditions in hand (Table 1, entry 17), the substrate scope of enantioselective
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allylic etherification reaction were examined and the results were summarized in Scheme 3. Firstly,
different ester groups including ethyl (5b), tertꢀbutyl (5c), benzyl (5d), 1ꢀadamantyl (5e) and
2
ꢀadamantyl (5f) esters were tested, and the product 7aaꢀ7fa could be afforded in comparable
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enantioselectivities (89ꢀ90% ee), while the yields were ranged from 60% to 79%. Either the
electronꢀwithdrawing groups or electronꢀdonating groups of the oꢀposition substituents on the
aromatic ring of MBH carbonates, the corresponding product 7gaꢀ7ka were obtained in 90% ee,
but lower yields (55ꢀ60%) were obtained for the MBH carbonates 5iꢀ5k with halogen substituents
on the aromatic ring. The methyl or methoxy groups (5lꢀ5m) on the mꢀposition of the phenyl ring
could afford the corresponding products (7laꢀ7ma) in higher ee values (91ꢀ92%), and the
electronꢀwithdrawing substitutions (5nꢀ5p) could give the products (7naꢀ7pa) in 83ꢀ86% ee
values. Moderate enantioselectivities (81ꢀ84% ee) and moderate to good yields (73ꢀ95%) were
obtained for the pꢀposition substituents on the aromatic ring of MBH carbonates. Moreover, when
2ꢀfuryl, 2ꢀthienyl and 3ꢀthienyl substituted MBH carbonates were used as the substrates, the
asymmetric allylic etherification reaction could afford the products (7vaꢀ7xa) in 75ꢀ92% yield and
88ꢀ92% ee. In the case of aliphatic MBH carbonate (5y), the corresponding product (7ya) was
obtained in 50% yield and 81% ee. When dimethylphenylsilanol (3b) was used as the nucleophile,
the product (7ab) was obtained in 60% yield with 87% ee. The absolute configuration of 7ka was
determined to be R configuration by Xꢀray crystallographic analysis (Figure 1).
Figure 1. Xꢀray crystal structure (R)ꢀ7ka. The thermal ellipsoid was drawn at the 50%
probability level.
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Scheme 4. Transformations of the allylic etherification products
As shown in Scheme 4a, the allylic etherification product 7ca could be transformed into the
corresponding alcohol 9ca in 95% yield and 90% ee in the presence of TBAF. Thus, when
Ph
3
3
SiOH was used as the nucleophile, Ph SiOH could be used as the water surrogate. In the
20
presence of the DIBALꢀH, the reduction of 7aa proceeded well, affording the desired reduction
21
product 10aa in 72% yield and 91% ee. The 1,3ꢀdipolar cycloaddition reaction of the allylic
etherification product 7aa with chlorobenzaldoxime was performed in DCM, and the cycloadduct
11aa was isolated in 90% yield, 4:1 dr and 92% ee (Scheme 4c).
Scheme 5. Proposed activation model for the formation of product (R)ꢀ7ka
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As shown in Scheme 5, on the basis of the experimental results, we proposed a probable
activation model for the formation of product (R)ꢀ7ka catalyzed by (DHQD) PYR. Firstly, a
2
cationic ammonium intermediate was formed from a Michael type addition reaction of nitrogen
2 2
atom of (DHQD) PYR with MBH carbonate 5k. The (DHQD) PYR–MBH adduct would be
2
2
preferentially formed as the E isomer. The MBH moiety in the Uꢀshape cleft of (DHQD)
2
PYR
such a sandwichꢀlike geometry was stabilized by the pꢀp stacking between the quinoline moiety
23
and phenyl ring which effectively blocked the Re face of this complex. Thus, the triphenylsilanol
anion was much more favorable attack from the Si face affording 7ka with the R configuration.
In conclusion, we have developed a novel and convenient chiral cinchona alkaloid
(
2 3
DHQD) PYR catalyzed enantioselective allylic etherification of MBH carbonates and Ph SiOH
i
o
with Pr
2
EtN as the base in MTBE at 90 C. A series of aromatic, heterocyclic or aliphatic MBH
carbonates (25 examples) worked well with triphenylsilanol, affording the corresponding
etherification products in high regioselectivities (>20:1), moderate to good yields (58ꢀ98%) and
good enantioselectivities (up to 92%). When dimethylphenylsilanol was used as the nucleophile,
3
the product 7ba was obtained in 60% yield, and 87% ee. Thus, when Ph SiOH was used as the
3
nucleophile, Ph SiOH could be used as the water surrogate and the chiral silicon contained
compounds could be obtained.
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EXPERIMENTAL SECTION
General Methods. All of the reagents and solvents were purchased from commercial sources,
and were used without further purification unless specified. The solvents (MTBE, THF) used in
the reaction were super dry solvents purchased from commercial sources and other solvents used
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in the reaction were dried by usual methods. Optical rotations were recorded with a sodium lamp
T
D
of wavelength 589 nm and reported as follows: [α]
(c = g/100 mL, solvent). Melting points
1
were recorded with a micro melting point apparatus and are uncorrected. H NMR spectra were
recorded on commercial instruments (600 MHz). Chemical shifts are recorded in ppm relative to
tetramethylsilane and with the solvent resonance as the internal standard. Data are reported as
follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet, br = broad,
1
3
q = quartet) coupling constants (Hz), integration. C NMR data were collected on commercial
instruments (150 or 100 MHz) with complete proton decoupling. Chemical shifts are reported in
ppm from the tetramethylsilane with the solvent resonance as internal standard. High resolution
mass spectra were taken with electrospray ionization (ESI) as the ionization method used for the
HRMS measurement. All experiments were monitored by analytical thin layer chromatography
(TLC). Enantiomeric excess were determined by chiral HPLC ODꢀH, IA or ID columns in
comparison with the authentic racemates. HPLC samples were dissolved in DCM : nꢀhexane = 1:4
unless otherwise stated. All reactions were carried out in a sealed pressure tube.
General procedure for the synthesis of 7aa-7ya and 7ab. In a dried pressure tube equipped
3 2
with a stirring bar, Ph SiOH (13.8 mg, 0.05 mmol), 5aꢀ5y (0.075 mmol), (DHQD) PYR (4.4 mg,
i
0.005 mmol), Pr EtN (8.3 µL, 0.05 mmol), and MTBE (0.4 mL) were added. The mixture was
2
o
sealed and heated at 90 C for 12 h. After the completion of the reaction (as monitored by TLC),
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and the resulting mixture was cooled to room temperature. The reaction mixture was extracted
2 4
with diethyl ether. The organic layers were collected, dried over anhydrous Na SO , filtered and
concentrated under reduced pressure. The crude material was purified by column chromatography
on silica gel using VEA :VPE = 1:100 as eluent.
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Triphenylsilanol (3a). White solid; 4.8 mg, 7% yield. Mp 150ꢀ152 C. H NMR (600 MHz,
13
CDCl ) δ 7.68ꢀ7.59 (m, 6H), 7.47ꢀ7.42 (m, 3H), 7.39 (t, J = 7.2 Hz, 6H), 2.62 (s, 1H). C NMR
3
+
(
150 MHz, CDCl
3
) δ 135.3, 135.1, 130.3, 128.1. HRMS: calcd for C18
H16OSiNa [M + Na]
2
99.0863, found 299.0864.
Methyl 2ꢀ((4ꢀbromophenyl)((triphenylsilyl)oxy)methyl)acrylate (4a). White solid; Mp 146ꢀ147
o
1
C. H NMR (600 MHz, CDCl
3
) δ 7.51 (d, J = 7.2 Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.33 (t, J =
7
1
.2 Hz, 6H), 7.29 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 8.4 Hz, 2H), 6.29 (s, 1H), 6.28 (s, 1H), 5.71 (s,
13
H), 3.57 (s, 3H). C NMR (100 MHz, CDCl
3
) δ 165.9, 142.7, 140.9, 135.5, 133.8, 131.2, 130.3,
+
129.2, 128.0, 124.8, 121.5, 73.2, 51.8. HRMS calcd for C29
found 551.0658.
H25BrO
3
SiNa [M + Na] 551.0649,
Adamantanꢀ1ꢀyl 2ꢀ(((tertꢀbutoxycarbonyl)oxy)(phenyl)methyl)acrylate (5e). White solid; Mp
o
1
1
19ꢀ121 C. H NMR (600 MHz, CDCl ) δ 7.38 (d, J = 7.8 Hz, 2H), 7.33 (t, J = 7.2 Hz, 2H), 7.29
3
(t, J = 7.2 Hz, 1H), 6.42 (s, 1H), 6.32 (s, 1H), 5.79 (s, 1H), 2.12 (s, 3H), 2.02 (q, J = 11.4 Hz, 6H),
13
1
.62ꢀ1.59 (m, 6H), 1.46 (s, 9H). C NMR (150 MHz, CDCl
3
) δ 163.9, 152.6, 141.2, 137.9, 128.5,
+
32 5
128.0, 124.7, 82.6, 81.7, 76.3, 41.2, 36.2, 30.9, 27.9. HRMS calcd for C25H O Na [M + Na]
4
35.2142, found 435.2141.
Adamantanꢀ2ꢀyl 2ꢀ(((tertꢀbutoxycarbonyl)oxy)(phenyl)methyl)acrylate (5f). White solid; Mp
o
1
1
3
09ꢀ111 C. H NMR (600 MHz, CDCl ) δ 7.40 (d, J = 7.2 Hz, 2H), 7.33 (t, J = 7.2 Hz, 2H), 7.29
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(
t, J = 7.2 Hz, 1H), 6.51 (s, 1H), 6.48 (s, 1H), 5.88 (s, 1H), 4.97ꢀ4.90 (m, 1H), 2.00ꢀ1.93 (m, 2H),
1
.90 (s, 1H), 1.84ꢀ1.69 (m, 9H), 1.63 (d, J = 5.4 Hz, 1H), 1.53 (d, J = 11.4 Hz, 1H), 1.46 (s, 9H).
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3
C NMR (150 MHz, CDCl ) δ 164.5, 152.6, 140.1, 137.8, 128.6, 127.9, 126.1, 82.7, 78.2, 76.1,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
32 5
7.4, 36.41, 36.37, 31.93, 31.89, 31.8, 31.7, 27.9, 27.3, 27.1. HRMS calcd for C25H O Na [M +
+
Na] 435.2142, found 435.2139.
Methyl (S)ꢀ2ꢀ(phenyl((triphenylsilyl)oxy)methyl)acrylate (7aa). White solid; 20.4 mg, 91%
25
o
1
yield; 90% ee. [α]
D
= +83.2 (c 0.67, DCM). Mp 101ꢀ104 C. H NMR (600 MHz, CDCl
3
): δ 7.51
(d, J = 7.2 Hz, 6H), 7.40 (t, J = 7.2 Hz, 3H), 7.32 (t, J = 7.2 Hz, 6H), 7.23ꢀ7.15 (m, 5H), 6.28 (s,
1
3
1
3
H), 6.26 (s, 1H), 5.77 (s, 1H), 3.55 (s, 3H). C NMR (150 MHz, CDCl ) δ 166.1, 143.3, 141.8,
1
26 3
35.6, 134.1, 130.1, 128.1, 127.9, 127.6, 127.4, 124.6, 73.9, 51.7. HRMS calcd for C29H O SiNa
+
[M + Na] 473.1543, found 473.1547. The ee was determined by HPLC (ID, MTBE/nꢀhexane =
2
/98, flow rate 0.6 mL/min, λ = 250 nm, tmajor = 17.6 min, tminor = 22.6 min).
Ethyl (S)ꢀ2ꢀ(phenyl((triphenylsilyl)oxy)methyl)acrylate (7ba). White solid; 17.6 mg, 76% yield;
25
o
1
9
0% ee. [α]
D 3
= +53.5 (c 0.67, DCM). Mp 102ꢀ104 C. H NMR (600 MHz, CDCl ) δ 7.53 (d, J =
7.2 Hz, 6H), 7.41 (t, J = 7.2 Hz, 3H), 7.32 (t, J = 7.2 Hz, 6H), 7.24ꢀ7.15 (m, 5H), 6.29 (s, 1H),
13
6
.26 (s, 1H), 5.78 (s, 1H), 4.10ꢀ3.93 (m, 2H), 1.12 (t, J = 7.2 Hz, 3H). C NMR (150 MHz,
CDCl
3
) δ 165.7, 143.5, 141.9, 135.6, 134.1, 130.1, 128.1, 127.9, 127.53, 127.47, 124.4, 73.9, 60.6,
+
1
4.1. HRMS calcd for C30
H
28
O
3
SiNa [M + Na] 487.1700, found 487.1710. The ee was
determined by HPLC (ID, MTBE/nꢀhexane = 2/98, flow rate 0.8 mL/min, λ = 250 nm, tmajor = 8.6
min, tminor = 10.6 min).
tertꢀButyl (S)ꢀ2ꢀ(phenyl((triphenylsilyl)oxy)methyl)acrylate (7ca). Colorless oil; 14.8 mg, 60%
25
yield; 90% ee (measured after desilylation to the corresponding alcohol 9ca). [α]
D
= +99.6 (c
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.67, DCM). H NMR (600 MHz, CDCl ) δ 7.53 (d, J = 6.6 Hz, 6H), 7.40 (t, J = 7.2 Hz, 3H), 7.32
3
1
3
(
t, J = 7.2 Hz, 6H), 7.22ꢀ7.15 (m, 5H), 6.21 (s, 1H), 6.18 (s, 1H), 5.72 (s, 1H), 1.27 (s, 9H). C
NMR (150 MHz, CDCl
3
) δ 164.9, 144.8, 142.0, 135.6, 134.2, 130.1, 128.0, 127.9, 127.5, 127.4,
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60
+
1
23.6, 80.9, 74.1, 28.0. HRMS calcd for C32
H
32
O
3
SiNa [M + Na] 515.2013, found 515.2017.
Benzyl (S)ꢀ2ꢀ(phenyl((triphenylsilyl)oxy)methyl)acrylate (7da). Colorless oil; 20.8 mg, 79%
25
D
1
yield; 90% ee. [α] = +63.0 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.52 (d, J = 7.2 Hz,
3
6
H), 7.41 (t, J = 7.2 Hz, 3H), 7.37ꢀ7.27 (m, 9H), 7.23ꢀ7.17 (m, 5H), 7.14 (dd, J = 6.6, 3.6 Hz, 2H),
13
6
.35 (s, 1H), 6.30 (s, 1H), 5.81 (s, 1H), 5.06 (d, J = 12.6, 1H), 4.95 (d, J = 12.6, 1H). C NMR
(150 MHz, CDCl
3
) δ 165.5, 143.2, 141.7, 135.9, 135.6, 134.0, 130.1, 128.5, 128.1, 128.0, 127.9,
+
127.6, 127.5, 125.0, 73.9, 66.3. HRMS calcd for C35
30
H O
3
SiNa [M + Na] 549.1856, found
5
49.1870. The ee was determined by HPLC (IA, 2ꢀpropanol/nꢀhexane = 3/97, flow rate 0.5
mL/min, λ = 250 nm, tmajor = 11.3 min, tminor = 17.6 min).
Adamantanꢀ1ꢀyl 2ꢀ((S)ꢀphenyl((triphenylsilyl)oxy)methyl)acrylate (7ea). Colorless oil; 18.8 mg,
25
D
6
6% yield; 89% ee (measured after desilylation to the corresponding alcohol 9ea). [α]
= +69.4
1
(c 0.67, DCM). H NMR (600 MHz, CDCl
3
) δ 7.53 (d, J = 6.6 Hz, 6H), 7.40 (t, J = 7.2 Hz, 3H),
7
.32 (t, J = 7.2 Hz, 6H), 7.24ꢀ7.11 (m, 5H), 6.21 (s, 1H), 6.18 (s, 1H), 5.72 (s, 1H), 2.08 (s, 3H),
1
3
1.91 (q, J = 11.4 Hz, 6H), 1.61ꢀ1.56 (m, 6H). C NMR (150 MHz, CDCl
3
) δ 164.6, 144.8, 142.1,
1
35.6, 134.2, 130.1, 128.0, 127.9, 127.5, 127.4, 123.6, 81.0, 74.1, 41.2, 36.3, 30.9. HRMS calcd
+
38 3
for C38H O SiNa [M + Na] 593.2482, found 593.2491.
Adamantanꢀ2ꢀyl 2ꢀ((S)ꢀphenyl((triphenylsilyl)oxy)methyl)acrylate (7fa). Colorless oil; 20 mg,
25
70% yield; 90% ee (measured after desilylation to the corresponding alcohol 9fa). [α] = +52.7
D
1
(
c 0.67, DCM). H NMR (600 MHz, CDCl
3
) δ 7.53 (d, J = 6.6 Hz, 6H), 7.40 (t, J = 7.2 Hz, 3H),
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.32 (t, J = 7.2 Hz, 6H), 7.25ꢀ7.12 (m, 5H), 6.34 (s, 1H), 6.27 (s, 1H), 5.80 (s, 1H), 4.80ꢀ4.76 (m,
13
3
H), 1.84ꢀ1.65 (m, 12H), 1.43 (d, J = 12.0 Hz, 2H). C NMR (150 MHz, CDCl ) δ 165.0, 143.8,
41.9, 135.6, 134.1, 130.1, 128.2, 127.9, 127.6, 127.5, 124.4, 100.1, 77.5, 74.0, 37.5, 36.3, 31.84,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
+
1.76, 31.73, 27.3, 27.1. HRMS calcd for C38
H
38
O
3
SiNa [M + Na] 593.2482, found 593.2491.
Methyl (S)ꢀ2ꢀ(oꢀtolyl((triphenylsilyl)oxy)methyl)acrylate (7ga). White solid; 20.2 mg, 87%
25
D
o
1
yield; 90% ee. [α] = +80.6 (c 0.67, DCM). Mp 102ꢀ105 C. H NMR (600 MHz, CDCl ) δ 7.53
3
(d, J = 7.2 Hz, 6H), 7.48 (d, J = 7.8 Hz, 1H), 7.41 (t, J = 7.2 Hz, 3H), 7.33 (t, J = 7.2 Hz, 6H),
7
1
1
4
.19ꢀ7.09 (m, 2H), 6.98 (d, J = 7.2 Hz, 1H), 6.31 (s, 1H), 6.07 (s, 1H), 6.00 (s, 1H), 3.53 (s, 3H),
1
3
.96 (s, 3H). C NMR (150 MHz, CDCl
3
) δ 166.5, 143.0, 139.4, 135.8, 135.6, 134.2, 130.3, 130.1,
+
28 3
28.2, 127.9, 127.5, 125.9, 125.4, 70.7, 51.7, 18.9. HRMS calcd for C30H O SiNa [M + Na]
87.1700, found 487.1705. The ee was determined by HPLC (ID, MTBE/nꢀhexane = 2/98, flow
rate 0.5 mL/min, λ = 250 nm, tmajor = 18.5 min, tminor = 20.7 min).
Methyl (S)ꢀ2ꢀ((2ꢀmethoxyphenyl)((triphenylsilyl)oxy)methyl)acrylate (7ha). Colorless oil; 16.8
25
1
mg, 70% yield; 90% ee. [α]
6.6 Hz, 6H), 7.46 (dd, J = 7.2, 1.8 Hz, 1H), 7.39 (t, J = 7.2 Hz, 3H), 7.31 (t, J = 7.2 Hz, 6H),
.23ꢀ7.15 (m,1H), 6.90 (t, J = 7.2 Hz, 1H), 6.66 (d, J = 7.8 Hz, 1H), 6.32 (s, 1H), 6.29 (s, 1H),
D 3
= +40.1 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.54 (d, J =
7
1
3
6.09 (s, 1H), 3.53 (s, 3H), 3.46 (s, 3H). C NMR (150 MHz, CDCl
3
) δ 166.4, 156.4, 143.0, 135.6,
134.6, 130.2, 129.9, 128.8, 128.2, 127.7, 125.4, 120.4, 110.4, 67.4, 55.0, 51.6. HRMS calcd for
+
C
30 28 4
H O SiNa [M + Na] 503.1649, found 503.1654. The ee was determined by HPLC (ODꢀH,
2
ꢀpropanol/nꢀhexane = 5/95, flow rate 0.8 mL/min, λ = 250 nm, tmajor = 5.6 min, tminor = 13.1 min).
Methyl (R)ꢀ2ꢀ((2ꢀfluorophenyl)((triphenylsilyl)oxy)methyl)acrylate (7ia). White solid; 14.0 mg,
25
D
o
1
60% yield; 90% ee. [α]
3
= +77.9 (c 0.67, DCM). Mp 114ꢀ116 C. H NMR (600 MHz, CDCl ) δ
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.55 (d, J = 7.2 Hz, 6H), 7.41 (t, J = 7.2 Hz, 4H), 7.33 (t, J = 7.2 Hz, 6H), 7.16 (dd, J = 13.8, 6.6
Hz), 7.04 (t, J = 7.2 Hz, 1H), 6.83 (t, J = 9.0 Hz, 1H), 6.39 (s, 1H), 6.27 (s, 1H), 6.10 (s, 1H), 3.56
1
3
(
s, 3H). C NMR (150 MHz, CDCl
3
) δ 165.9, 160.0 (d, JC-F = 247.5 Hz), 142.1, 135.5, 133.9,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
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28
29
30
31
32
33
34
35
36
37
38
39
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41
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1
1
30.2, 129.33 (d, JC-F = 6.0 Hz), 129.29 (d, JC-F = 1.5 Hz), 128.9 (d, JC-F = 12.0 Hz), 127.9, 125.7,
23.9 (d, JC-F = 3.0 Hz), 115.3 (d, JC-F = 22.5 Hz), 67.6 (d, JC-F = 1.5 Hz), 51.7. HRMS calcd for
+
C H FO SiNa [M + Na] 491.1449, found 491.1456. The ee was determined by HPLC (ID,
2
9
25
3
MTBE/nꢀhexane = 3/97, flow rate 0.9 mL/min, λ = 250 nm, tmajor = 12.2 min, tminor = 17.4 min).
Methyl (R)ꢀ2ꢀ((2ꢀchlorophenyl)((triphenylsilyl)oxy)methyl)acrylate (7ja). White solid; 13.3 mg,
25
_
o
1
5
7
7
D 3
5% yield; 90% ee. [α] = 14.9 (c 0.67, DCM). Mp 120ꢀ123 C. H NMR (600 MHz, CDCl ) δ
.61 (d, J = 7.8 Hz, 1H), 7.55 (d, J = 7.8 Hz, 6H), 7.41 (t, J = 7.2 Hz, 3H), 7.33 (t, J = 7.2 Hz, 6H),
.24ꢀ7.17 (m, 2H), 7.14 (t, J = 7.2 Hz 1H), 6.34 (s, 1H), 6.23 (s, 1H), 5.98 (s, 1H), 3.53 (s, 3H).
13
3
C NMR (100 MHz, CDCl ) δ 166.0, 142.1, 139.1, 135.6, 133.9, 133.01, 130.1, 129.5, 129.3,
+
128.8, 127.9, 126.8, 126.5, 70.4, 51.7. HRMS calcd for C29
H25ClO
3
SiNa [M + Na] 507.1154,
found 507.1158. The ee was determined by HPLC (ODꢀH, 2ꢀpropanol/nꢀhexane = 5/95, flow rate
0.8 mL/min, λ = 250 nm, tmajor = 5.4 min, tminor = 9.9 min).
Methyl (R)ꢀ2ꢀ((2ꢀbromophenyl)((triphenylsilyl)oxy)methyl)acrylate (7ka). White solid; 15.3
25
o
1
mg, 58% yield; 90% ee. [α]
D 3
= +3.5 (c 0.67, DCM). Mp 122ꢀ125 C. H NMR (600 MHz, CDCl )
δ 7.62 (d, J = 7.8 Hz, 1H), 7.54 (d, J = 7.8 Hz, 6H), 7.42ꢀ7.35 (m, 4H), 7.32 (t, J = 7.2 Hz, 6H),
7.25ꢀ7.23 (m, 1H), 7.06 (t, J = 7.2 Hz, 1H), 6.32 (s, 1H), 6.18 (s, 1H), 5.89 (s, 1H), 3.51 (s, 3H).
13
C NMR (100 MHz, CDCl
3
) δ 166.1, 142.2, 140.7, 135.6, 134.0, 132.6, 130.1, 129.8, 129.1,
+
127.9, 127.4, 126.7, 123.3, 72.8, 51.8. HRMS calcd for C H BrO SiNa [M + Na] 551.0649,
29
25
3
found 551.0654. The ee was determined by HPLC (ODꢀH, 2ꢀpropanol/nꢀhexane = 5/95, flow rate
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0
.8 mL/min, λ = 250 nm, tmajor = 5.3 min, tminor = 11.6 min).
Methyl (S)ꢀ2ꢀ(mꢀtolyl((triphenylsilyl)oxy)methyl)acrylate (7la). White solid; 18.8 mg, 81%
25
o
1
yield; 92% ee. [α]
D 3
= +72.4 (c 0.67, DCM). Mp 81ꢀ83 C. H NMR (600 MHz, CDCl ) δ 7.53 (d,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
J = 7.8 Hz, 6H), 7.41 (t, J = 7.2 Hz, 3H), 7.33 (t, J = 7.2 Hz, 6H), 7.09 (t, J = 7.2 Hz, 1H), 7.03 (d,
J = 7.8 Hz, 1H), 6.99 (d, J = 7.2 Hz, 1H), 6.95 (s, 1H), 6.30 (s, 1H), 6.27 (s, 1H), 5.75 (s, 1H),
13
3
1
.57 (s, 3H), 2.23 (s, 3H). C NMR (150 MHz, CDCl ) δ 166.1, 143.2, 141.6, 137.5, 135.6, 134.1,
3
28 3
30.1, 128.3, 128.0, 127.8, 124.6, 124.5, 73.9, 51.7, 21.5. HRMS calcd for C30H O SiNa
+
[M+Na] 487.1700, found 487.1708. The ee was determined by HPLC (ID, MTBE/nꢀhexane =
2
/98, flow rate 0.6 mL/min, λ = 250 nm, tmajor = 18.1 min, tminor = 23.0 min).
Methyl (S)ꢀ2ꢀ((3ꢀmethoxyphenyl)((triphenylsilyl)oxy)methyl)acrylate (7ma). Colorless oil;
25
1
18.0 mg, 75% yield; 91% ee. [α] = +100.1 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.55
D
3
(d, J = 7.2 Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.34 (t, J = 7.2 Hz, 6H), 7.12 (t, J = 7.8 Hz, 1H), 6.83
(d, J = 7.8 Hz, 1H), 6.79 (s, 1H), 6.74 (dd, J = 8.4, 1.8 Hz, 1H), 6.30 (s, 1H), 6.25 (s, 1H), 5.78 (s,
13
1H), 3.70 (s, 3H), 3.58 (s, 3H). C NMR (150 MHz, CDCl
3
) δ 166.1, 159.4, 143.4, 143.2, 135.6,
134.1, 130.1, 129.1, 127.9, 124.8, 119.8, 113.5, 112.6, 73.7, 55.2, 51.7. HRMS calcd for
+
C H O SiNa [M + Na] 503.1649, found 503.1656. The ee was determined by HPLC (ODꢀH,
3
0
28
4
2ꢀproprnol/nꢀhexane = 3/97, flow rate 0.5 mL/min, λ = 250 nm, tmajor = 9.2 min, tminor = 10.8 min).
Methyl (S)ꢀ2ꢀ((3ꢀfluorophenyl)((triphenylsilyl)oxy)methyl)acrylate (7na). White solid; 19.2 mg,
25
o
1
82% yield; 84% ee. [α]
D 3
= +81.8 (c 0.67, DCM). Mp 96ꢀ98 C. H NMR (600 MHz, CDCl ) δ
7
.52 (d, J = 7.8 Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.33 (t, J = 7.2 Hz, 6H), 7.13 (dd, J = 13.8, 7.8
Hz, 1H), 6.98 (d, J = 7.8 Hz, 1H), 6.93 (d, J = 9.6 Hz, 1H), 6.86 (td, J = 8.4, 1.8 Hz, 1H), 6.31 (s,
13
1H), 6.28 (s, 1H), 5.75 (s, 1H), 3.58 (s, 3H). C NMR (150 MHz, CDCl
3
) δ 165.9, 162.7 (d, JC-F
=
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44.5 Hz), 144.5 (d, JC-F = 6.0 Hz), 142.8, 135.5, 133.8, 130.3, 129.5 (d, JC-F = 7.5 Hz), 128.0,
25.1, 123.0 (d, JC-F = 3.0 Hz), 114.5 (d, JC-F = 21.0 Hz), 114.2 (d, JC-F = 22.5 Hz), 73.2 (d, JC-F
=
+
.5 Hz), 51.8. HRMS calcd for C29
H
25FO
3
SiNa [M + Na] 491.1449, found 491.1452. The ee was
10
11
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53
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55
56
57
58
59
60
determined by HPLC (ID, MTBEl/nꢀhexane = 2/98, flow rate 0.6 mL/min, λ = 250 nm, tmajor
6.5 min, tminor = 20.2 min).
S)ꢀ2ꢀ((3ꢀchlorophenyl)((triphenylsilyl)oxy)methyl)acrylate (7oa). White solid; 20.8 mg, 86%
=
1
(
25
o
1
yield; 86% ee. [α]
D 3
= +93.6 (c 0.67, DCM). Mp 81ꢀ83 C. H NMR (600 MHz, CDCl ) δ 7.52 (d,
J = 7.8 Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.34 (t, J = 7.2 Hz, 6H), 7.21ꢀ7.02 (m, 4H), 6.33 (s, 1H),
1
3
6
1
3
.30 (s, 1H), 5.72 (s, 1H), 3.58 (s, 3H). C NMR (150 MHz, CDCl ) δ 165.8, 143.9, 142.7, 135.5,
33.9, 133.7, 130.3, 129.4, 128.0, 127.7, 127.6, 125.6, 125.1, 73.2, 51.8. HRMS calcd for
+
C H ClO SiNa [M + Na] 507.1154, found 507.1160. The ee was determined by HPLC (ID,
29 25
3
MTBE/nꢀhexane = 2/98, flow rate 1.0 mL/min, λ = 250 nm, tmajor = 9.8 min, tminor = 11.7 min).
Methyl (S)ꢀ2ꢀ((3ꢀbromophenyl)((triphenylsilyl)oxy)methyl)acrylateethyl (7pa). Colorless oil;
25
1
2
D 3
1.6 mg, 82% yield; 83% ee; [α] = +71.2 (c 0.67, DCM); H NMR (600 MHz, CDCl ) δ 7.53 (d,
J = 7.2 Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.34 (t, J = 7.2 Hz, 6H), 7.32ꢀ7.27 (m, 2H), 7.13 (d, J =
13
7
.8 Hz, 1H), 7.04 (t, J = 7.2 Hz, 1H), 6.33 (s, 1H), 6.31 (s, 1H), 5.71 (s, 1H), 3.58 (s, 3H).
C
3
NMR (150 MHz, CDCl ) δ 165.8, 144.1, 142.6, 135.5, 133.7, 130.7, 130.6, 130.3, 129.7, 128.0,
+
1
26.1, 125.1, 122.1, 73.2, 51.8. HRMS calcd for C29
3
H25BrO SiNa [M + Na] 551.0649, found
551.0654. The ee was determined by HPLC (ID, MTBE/nꢀhexane = 2/98, flow rate 0.6 mL/min, λ
=
250 nm, tmajor = 16.0 min, tminor = 18.5 min).
Methyl (S)ꢀ2ꢀ(pꢀtolyl((triphenylsilyl)oxy)methyl)acrylate (7qa). White solid; 22.0 mg, 95%
25
o
1
yield; 81% ee. [α]
D 3
= +92.1 (c 0.67, DCM). Mp 78ꢀ80 C. H NMR (600 MHz, CDCl ) δ 7.54 (d,
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J = 7.8 Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.33 (t, J = 7.2 Hz, 6H), 7.12 (d, J = 7.8 Hz, 2H), 7.02 (d,
13
J = 7.8 Hz, 2H), 6.28 (s, 1H), 6.26 (s, 1H), 5.77 (s, 1H), 3.56 (s, 3H), 2.31 (s, 3H). C NMR (100
3
MHz, CDCl ) δ 166.1, 143.3, 138.8, 137.2, 135.6, 134.1, 130.1, 128.8, 127.9, 127.4, 124.4, 73.7,
0
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3
4
5
6
7
8
9
0
1
2
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5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
+
5
1.7, 21.3. HRMS calcd for C30
H
28
O
3
SiNa [M + Na] 487.1700, found 487.1707. The ee was
determined by HPLC (ID, 2ꢀpropanol/nꢀhexane = 3/97, flow rate 0.5 mL/min, λ = 250 nm, tmajor
=
9
.2 min, tminor = 10.2 min).
Methyl (S)ꢀ2ꢀ((4ꢀmethoxyphenyl)((triphenylsilyl)oxy)methyl)acrylate (7ra). Colorless oil; 17.5
25
1
mg, 73% yield; 84% ee. [α]
D 3
= +109.9 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.53 (d, J
=
7.8 Hz, 6H), 7.41 (t, J = 7.2 Hz, 3H), 7.33 (t, J = 7.2 Hz, 6H), 7.12 (d, J = 8.4 Hz, 2H), 6.73 (d,
13
J = 8.4 Hz, 2H), 6.28 (s, 1H), 6.27 (s, 1H), 5.74 (s, 1H), 3.77 (s, 3H), 3.57 (s, 3H). C NMR (100
MHz, CDCl ) δ 166.1, 159.0, 143.3, 135.5, 134.1, 133.9, 130.1, 128.7, 127.9, 124.1, 113.4, 73.4,
3
+
5
5.3, 51.7. HRMS calcd for C30
H
28
O
4
SiNa [M + Na] 503.1649, found 503.1659. The ee was
determined by HPLC (ID, 2ꢀpropanol/nꢀhexane = 3/97, flow rate 0.5 mL/min, λ = 250 nm, tmajor
=
1
1.5 min, tminor = 13.0 min).
Methyl (S)ꢀ2ꢀ((4ꢀfluorophenyl)((triphenylsilyl)oxy)methyl)acrylate (7sa). White solid; 20.4 mg,
25
D
o
1
8
7% yield; 83% ee. [α] = +69.5 (c 0.67, DCM). Mp 69ꢀ72 C. H NMR (600 MHz, CDCl ) δ
3
7.52 (d, J = 7.8 Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.34 (t, J = 7.2 Hz, 6H), 7.16 (dd, J = 7.8, 5.4 Hz,
13
2
H), 6.86 (t, J = 8.4 Hz, 2H), 6.31 (s, 2H), 5.76 (s, 1H), 3.58 (s, 3H). C NMR (150 MHz, CDCl
3
)
δ 166.0, 162.2 (d, JC-F = 244.5 Hz), 143.1, 137.7 (d, JC-F = 3.0 Hz), 135.5, 133.9, 130.2, 129.1 (d,
J
3
C-F = 7.5 Hz), 127.9, 124.5, 114.9 (d, JC-F = 21 Hz), 73.2, 51.7. HRMS calcd for C29H25FO SiNa
+
[M + Na] 491.1449, found 491.1465. The ee was determined by HPLC (ID, 2ꢀpropanol/nꢀhexane
=
3/97, flow rate 0.5 mL/min, λ = 250 nm, tminor = 8.8 min, tmajor = 9.8 min).
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Methyl (S)ꢀ2ꢀ((3,4ꢀdimethylphenyl)((triphenylsilyl)oxy)methyl)acrylate (7ta). White solid; 23.4
25
o
1
mg, 98% yield; 88% ee. [α]
D
= +100.7 (c 0.67, DCM). Mp 104ꢀ106 C. H NMR (600 MHz,
3
CDCl ) δ 7.51 (d, J = 7.8 Hz, 6H), 7.40 (t, J = 7.2 Hz, 3H), 7.31 (t, J = 7.2 Hz, 6H), 6.95 (t, J =
10
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59
60
7
.8 Hz, 2H), 6.88 (s, 1H), 6.27 (s, 1H), 6.24 (s, 1H), 5.72 (s, 1H), 3.55 (s, 3H), 2.19 (s, 3H), 2.12
13
(
s, 3H). C NMR (150 MHz, CDCl
3
) δ 166.2, 143.3, 139.1, 136.1, 135.8, 135.6, 135.3, 134.2,
130.0, 129.3, 128.9, 127.8, 124.9, 124.4, 73.8, 51.7, 19.8, 19.6. HRMS calcd for C H O SiNa
31
30
3
+
[M + Na] 501.1856, found 501.1867. The ee was determined by HPLC (ID, MTBE/nꢀhexane =
2
/98, flow rate 1.0 mL/min, λ = 250 nm, tmajor = 7.7 min, tminor = 9.9 min).
Methyl (S)ꢀ2ꢀ((3,4ꢀdimethoxyphenyl)((triphenylsilyl)oxy)methyl)acrylate (7ua). Colorless oil;
25
1
18.6 mg, 73% yield; 85% ee. [α]
D 3
= +127.4 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.52
(d, J = 7.8 Hz, 6H), 7.40 (t, J = 7.2 Hz, 3H), 7.32 (t, J = 7.2 Hz, 6H), 6.74ꢀ6.65 (m, 3H), 6.28 (s,
13
1H), 6.24 (s, 1H), 5.73 (s, 1H), 3.83 (s, 3H), 3.70 (s, 3H), 3.57 (s, 3H). C NMR (150 MHz,
CDCl
3
) δ 166.3, 148.5, 148.4, 143.3, 135.6, 134.3, 134.2, 130.1, 127.9, 124.2, 119.9, 110.8, 110.7,
+
73.8, 55.9, 55.8, 51.7. HRMS calcd for C31
H
30
O
5
SiNa [M + Na] 533.1755, found 533.1769. The
ee was determined by HPLC (ID, MTBE/nꢀhexane = 1/99, flow rate 0.5 mL/min, λ = 250 nm,
tmajor = 26.1 min, tminor = 30.9 min).
Methyl (R)ꢀ2ꢀ(furanꢀ2ꢀyl((triphenylsilyl)oxy)methyl)acrylate (7va). Colorless oil; 20.2 mg, 92%
25
1
yield; 92% ee. [α]
D 3
= +117.6 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.57 (d, J = 7.8 Hz,
6H), 7.42 (t, J = 7.2 Hz, 3H), 7.35 (t, J = 7.2 Hz, 6H), 7.24 (s, 1H), 6.40 (s, 1H), 6.32 (s, 1H),
13
6
.23ꢀ6.17 (m, 1H), 6.00 (d, J = 2.4 Hz, 1H), 5.82 (s, 1H), 3.60 (s, 3H). C NMR (150 MHz,
(CD ) CO) δ 166.0, 154.9, 143.3, 141.5, 136.2, 134.7, 131.1, 128.8, 126.2, 111.1, 108.8, 67.8,
3
2
+
24 4
52.0. HRMS calcd for C27H O SiNa [M + Na] 463.1336, found 463.1343. The ee was
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6
determined by HPLC (ID, MTBE/nꢀhexane = 1.5/98.5, flow rate 0.9 mL/min, λ = 250 nm, tmajor
=
1
3.6 min, tminor = 17.3 min).
Methyl (R)ꢀ2ꢀ(thiophenꢀ2ꢀyl((triphenylsilyl)oxy)methyl)acrylate (7wa). Colorless oil; 17.1 mg,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
25
1
75% yield; 88% ee. [α]
D 3
= +101.1 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.58 (d, J = 7.2
Hz, 6H), 7.43 (t, J = 7.2 Hz, 3H), 7.35 (t, J = 7.2 Hz, 6H), 7.16 (d, J = 5.4 Hz, 1H), 6.81 (t, J = 4.2
13
Hz, 1H), 6.72 (d, J = 3.0 Hz, 1H), 6.31 (s, 2H), 6.07 (s, 1H), 3.61 (s, 3H). C NMR (150 MHz,
CDCl
3
) δ 165.8, 146.2, 142.9, 135.6, 133.8, 130.2, 127.9, 126.4, 125.4, 125.1, 125.0, 69.3, 51.8.
+
HRMS calcd for C27
H
24
O
3
SSiNa [M + Na] 479.1108, found 479.1114. The ee was determined by
HPLC (ID, MTBE/nꢀhexane = 3/97, flow rate 0.8 mL/min, λ = 250 nm, tmajor = 13.9 min, tminor
=
1
6.3 min).
Methyl (R)ꢀ2ꢀ(thiophenꢀ3ꢀyl((triphenylsilyl)oxy)methyl)acrylate (7xa). White solid; 19.4 mg,
25
o
1
85% yield; 92% ee. [α]
D 3
= +56.9 (c 0.67, DCM). Mp 66ꢀ68 C. H NMR (600 MHz, CDCl ) δ
7.56 (d, J = 7.8 Hz, 6H), 7.43 (t, J = 7.2 Hz, 3H), 7.35 (t, J = 7.2 Hz, 6H), 7.14 (dd, J = 4.2, 3.0 Hz,
H), 6.98 (d, J = 2.4 Hz, 1H), 6.95 (d, J = 4.8 Hz, 1H), 6.30 (s, 1H), 6.27 (s, 1H), 5.91 (s, 1H),
1
1
3
3.60 (s, 3H). C NMR (150 MHz, CDCl
3
) δ 166.1, 143.1, 142.9, 135.5, 134.0, 130.2, 127.9, 126.6,
+
1
25.3, 124.6, 122.5, 69.7, 51.7. HRMS calcd for C H O SSiNa [M + Na] 479.1108, found
2
7
24
3
479.1117. The ee was determined by HPLC (ID, MTBE/nꢀhexane = 3/97, flow rate 0.8 mL/min, λ
=
250 nm, tmajor = 14.1 min, tminor = 17.0 min).
Methyl (S)ꢀ2ꢀ(cyclohexyl((triphenylsilyl)oxy)methyl)acrylate (7ya). Colorless oil; 13.4 mg,
25
1
50% yield; 81% ee. [α]
D 3
= +20.9 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.60 (d, J = 7.2
Hz, 6H), 7.42 (t, J = 7.2 Hz, 3H), 7.36 (t, J = 7.2 Hz, 6H), 6.18 (s, 1H), 5.85 (s, 1H), 4.71 (d, J =
4
.8 Hz, 1H), 3.62 (s, 3H), 1.79 (d, J = 12.6 Hz, 1H), 1.73ꢀ1.57 (m, 3H), 1.55ꢀ1.50 (m, 1H), 1.46 (d,
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J = 12.6 Hz, 1H), 1.18ꢀ0.93 (m, 5H). C NMR (150 MHz, CDCl ) δ 166.7, 141.9, 135.8, 134.6,
3
1
32 3
30.0, 127.8, 126.7, 75.5, 51.7, 44.0, 29.4, 27.6, 26.6, 26.5, 26.4. HRMS calcd for C29H O SiNa
+
[
M + Na] 479.2013, found 479.2020.
10
11
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Methyl (S)ꢀ2ꢀ(((dimethyl(phenyl)silyl)oxy)(phenyl)methyl)acrylate (7ab). Colorless oil; 9.8 mg,
25
1
6
2
1
1
0% yield; 87% ee. [α]
D 3
= +76.7 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.52ꢀ7.46 (m,
H), 7.40ꢀ7.31 (m, 3H), 7.30ꢀ7.24 (m, 4H), 7.23ꢀ7.20 (m, 1H), 6.29 (s, 1H), 6.08 (s, 1H), 5.62 (s,
1
3
3
H), 3.63 (s, 3H), 0.292 (s, 1H), 0.287 (s, 1H). C NMR (150 MHz, CDCl ) δ 166.4, 143.5, 142.2,
37.7, 133.6, 129.7, 128.2, 127.9, 127.7, 127.4, 124.6, 73.1, 51.8, ꢀ1.0, ꢀ1.2. HRMS: calcd for
+
C
H
19 22
O
3
SiNa [M + Na] 349.1230, found 349.1236. The ee was determined by HPLC (ODꢀH,
MTBE/nꢀhexane = 1/99, flow rate 0.8 mL/min, λ = 250 nm, tmajor = 11.6 min, tminor = 18.3 min).
1
Methyl (E)ꢀ3ꢀphenylꢀ2ꢀ(((triphenylsilyl)oxy)methyl)acrylate (8aa). H NMR (600 MHz, CDCl )
3
δ 7.86 (s, 1H), 7.67 (d, J = 7.2 Hz, 6H), 7.54 (d, J = 7.8 Hz, 2H), 7.44 (t, J = 7.2 Hz, 3H), 7.38 (t, J
1
3
= 7.2 Hz, 6H), 7.32 (t, J = 7.2 Hz, 1H), 7.28 (d, J = 7.8 Hz, 2H), 4.64 (s, 2H), 3.68 (s, 3H).
C
3
NMR (151 MHz, CDCl ) δ 168.2, 143.8, 135.6, 134.9, 134.2, 130.7, 130.2, 130.0, 129.3, 128.6,
+
128.0, 58.5, 52.0. HRMS: calcd for C29
H
26
O
3
SiNa [M + Na] 473.1543, found 473.1546.
Procedure of the products 7ca, 7ea, 7fa, 7ya desilylated to the corresponding alcohols. The
compound 7ca, 7ea, 7fa or 7ya was desilylated by adding tetrabutylammonium fluoride (1.0 equiv)
16
in THF. The mixture was stirred at room temperature. After the completion of the reaction (as
2
monitored by TLC), the mixture was quenched by adding 10 mL H O. The aqueous layer was
2 4
extracted 3 times with EtOAc, and the organic layers were dried over Na SO . The solvents were
removed in vacuo to give the crude mixture. The crude product was purified by flash column
chromatography using VDCM :VEA :VPE = 10:4:40 as the eluent to afford the allylic product.
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Enantiomeric excess was determined by HPLC with chiral stationary phase.
25
tertꢀButyl (S)ꢀ2ꢀ(hydroxy(phenyl)methyl)acrylate (9ca). Colorless oil; 11.1 mg, 95% yield;
2
5
D
1
90% ee. [α]
= +38.6 (c 0.67, DCM). H NMR (600 MHz, CDCl
3
) δ 7.38ꢀ7.33 (m, 4H), 7.28 (t, J
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
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5
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
=
7.2 Hz, 1H), 6.26 (s, 1H), 5.72 (s, 1H), 5.50 (d, J = 5.4 Hz, 1H), 3.07 (d, J = 6.0 Hz, 1H), 1.40 (s,
1
3
9
H). C NMR (150 MHz, CDCl
3
) δ 165.8, 143.5, 141.7, 128.5, 127.8, 126.7, 125.5, 81.8, 73.8,
+
2
8.1. HRMS calcd for C H O Na [M + Na] 257.1148, found 257.1152. The ee was determined
14
18
3
by HPLC (ODꢀH, 2ꢀpropanol/nꢀhexane = 5/95, flow rate 0.6 mL/min, λ = 250 nm, tmajor = 11.3
min, tminor = 12.5 min).
Adamantanꢀ1ꢀyl 2ꢀ((S)ꢀhydroxy(phenyl)methyl)acrylate (9ea). White solid; 15.0 mg, 96% yield;
25
o
1
8
D 3
9% ee. [α] = +9.2 (c 0.67, DCM). Mp 100ꢀ103 C. H NMR (600 MHz, CDCl ) δ 7.37ꢀ7.33
(
m, 4H), 7.28 (t, J = 7.2 Hz, 1H), 6.26 (s, 1H), 5.71 (s, 1H), 5.49 (d, J = 6.0 Hz, 1H), 3.12 (d, J =
13
6
.0 Hz, 1H), 2.14 (s, 3H), 2.09ꢀ1.98 (m, 6H), 1.66ꢀ1.61 (m, 6H). C NMR (150 MHz, CDCl
3
) δ
165.5, 143.5, 141.8, 128.5, 127.8, 126.6, 125.6, 82.0, 73.8, 41.3, 36.2, 30.9. HRMS calcd for
+
C H
20 24
O
3
Na [M + Na] 335.1618, found 335.1620. The ee was determined by HPLC (ODꢀH,
2ꢀpropanol/nꢀhexane = 5/95, flow rate 0.9 mL/min, λ = 250 nm, tmajor = 8.5 min, tminor = 10.2 min).
Adamantanꢀ2ꢀyl 2ꢀ((S)ꢀhydroxy(phenyl)methyl)acrylate (9fa). White solid; 15.3 mg, 98% yield;
25
_
o
1
90% ee. [α]
D 3
= 39.5 (c 0.67, DCM). Mp 74ꢀ76 C. H NMR (600 MHz, CDCl ) δ 7.39 (d, J =
7
.8 Hz, 2H), 7.34 (t, J = 7.2 Hz, 2H), 7.28 (t, J = 7.2 Hz, 1H), 6.42 (s, 1H), 5.83 (s, 1H), 5.58 (d, J
= 6.0 Hz, 1H), 5.01ꢀ4.91(m, 1H), 3.08 (d, J = 6.0 Hz, 1H), 1.95 (d, J = 18.6 Hz, 2H), 1.88 (d, J =
13
12.6 Hz, 1H), 1.85ꢀ1.77 (m, 5H), 1.76ꢀ1.70 (m, 4H), 1.52 (t, J = 10.8 Hz, 2H). C NMR (150
MHz, CDCl ) δ 165.8, 142.6, 141.6, 128.6, 127.9, 126.7, 126.1, 78.1, 73.7, 37.4, 36.4, 31.95,
3
+
3
1.93, 31.91, 31.88, 27.3, 27.0. HRMS calcd for C20
H
24
3
O Na [M + Na] 335.1618, found
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3
35.1618. The ee was determined by HPLC (ODꢀH, 2ꢀpropanol/nꢀhexane = 10/90, flow rate 0.8
mL/min, λ = 250 nm, tmajor = 7.0 min, tminor = 8.5 min).
Methyl (S)ꢀ2ꢀ(cyclohexyl((triphenylsilyl)oxy)methyl)acrylate (9ya). Colorless oil; 9.3 mg,
2
6
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
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58
59
60
2
5
_
1
9
5
1
D 3
4% yield; 81% ee. [α] = 4.36 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 6.25 (s, 1H),
.72 (s, 1H), 4.06 (t, J = 7.2 Hz, 1H), 3.78 (s, 3H), 2.53 (d, J = 7.8 Hz, 1H), 1.97 (d, J = 13.2 Hz,
13
H), 1.81ꢀ1.62 (m, 3H), 1.59ꢀ1.49 (m, 2H), 1.23ꢀ1.09 (m, 3H), 1.03ꢀ0.92 (m, 2H). C NMR (150
MHz, CDCl
3
) δ 167.3, 141.0, 126.4, 77.6, 52.0, 42.5, 30.1, 28.5, 26.5, 26.2, 26.1. HRMS: calcd
+
for C11
H
18
O
3
Na [M + Na] 221.1145, found 221.1146. The ee was determined by HPLC (ODꢀH,
2
ꢀpropanol/nꢀhexane = 10/90, flow rate 0.8 mL/min, λ = 250 nm, tminor = 5.8 min, tmajor = 6.3 min).
Procedure for the reduction of product 10aa. DIBALꢀH (1.0 M in PhMe, 0.12 mL, 0.12
o
mmol) was added dropwise to a stirred and cooled (ꢀ78 C) solution of 7aa (0.015 g, 0.033 mmol)
19
o
in DCM (0.5 mL). Stirring at ꢀ78 C was continued for 2.5 h and then MeOH (0.5 mL) was
added. The cooling bath was removed and a saturated aqueous solution of Rochelle’s salt was
added. The mixture was then extracted with ether. The combined organic extracts were washed
2 4
with brine, dried (Na SO ) and evaporated. The crude material was purified by column
chromatography on silica gel (eluting with Pet/EtOAc = 1/10 mixture), giving the desired product
10aa.
(
S)ꢀ2ꢀ(Phenyl((triphenylsilyl)oxy)methyl)propꢀ2ꢀenꢀ1ꢀol (10aa). (colorless oil; 10.0 mg, 72 %
2
5
1
yield; 91% ee. [α]
D 3
= +32.7 (c 0.67, DCM). H NMR (600 MHz, CDCl ) δ 7.58 (d, J = 6.6 Hz,
6
H), 7.42 (t, J = 7.2 Hz, 3H), 7.34 (t, J = 7.2 Hz, 6H), 7.30 (d, J = 7.2 Hz, 2H), 7.25ꢀ7.18 (m, 3H),
1
3
5.48 (s, 1H), 5.25 (s, 1H), 5.11 (s, 1H), 4.06 (d, J = 13.8 Hz, 1H), 3.87 (d, J = 13.8 Hz, 1H).
C
NMR (150 MHz, CDCl
3
) δ 150.1, 141.9, 135.6, 134.0, 130.2, 128.3, 127.9, 127.5, 126.5, 112.0,
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6
+
7
7.7, 62.9. HRMS: calcd for C H O SiNa [M + Na] 445.1594, found 445.1591. The ee was
2
8
26
2
determined by HPLC (ODꢀH, 2ꢀpropanol/nꢀhexane = 5/95, flow rate 0.8 mL/min, λ = 250 nm,
t
major = 9.1 min, tminor = 10.6 min).
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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9
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Procedure for the synthesis of cycloadduct 11aa. TEA (27 µL, 0.2 mmol) was added to a
o
20
solution of chlorobenzaldoxime (30.3 mg, 0.2 mmol) in anhydrous DCM (0.5 mL) at 0 C. After
stirring for 10 min a solution of 7aa (45 mg, 0.1 mmol) in anhydrous DCM was added dropwise.
The mixture was stirred at room temperature for 12 h. Then the reaction was quenched with water
(
5 mL) and the organic layer was separated. The aqueous layer was extracted with EtOAc. The
combined organic layers were dried with anhydrous Na SO and concentrated. Flash
15:1) afforded the
2
4
chromatography on silica gel (petroleum ether/ethyl acetate
=
diastereomerically product 11aa.
Methyl 3ꢀphenylꢀ5ꢀ((S)ꢀphenyl((triphenylsilyl)oxy)methyl)ꢀ4,5ꢀdihydroisoxazoleꢀ5ꢀcarboxylate
2
5
o
(11aa) White solid; 51.2mg, 90% yield; 92% ee. [α]
D
= +78.6 (c 0.67, DCM). Mp 124ꢀ127 C.
1
3
H NMR (600 MHz, CDCl ) δ (major diastereomer) 7.62ꢀ7.59 (m, 2H), 7.50ꢀ7.47 (m, 6H),
7.40ꢀ7.34 (m, 6H), 7.30ꢀ7.28 (m, 1H), 7.26ꢀ7.22 (m, 6H), 7.20ꢀ7.18 (m, 4H), 5.44 (s, 1H), 3.82 (d.
13
J = 16.8 Hz, 1H), 3.72 (d. J = 16.8 Hz, 1H), 3.57 (s, 3H). C NMR (150 MHz, CDCl ) δ (major
3
diastereomer) 170.6, 156.6, 137.7, 135.8, 133.6, 130.3, 130.1, 129.2, 128.7, 128.6, 128.3, 127.9,
+
1
27.8, 127.0, 94.0, 76.9, 52.8, 37.8. HRMS: calcd for C36
H
31NO
4
SiNa [M + Na] 592.1915, found
592.1909. The ee was determined by HPLC (ID, 2ꢀpropanol/nꢀhexane = 5/95, flow rate 0.8
mL/min, λ = 250 nm, tminor = 17.1 min, tmajor = 26.0 min).
ASSOCIATED CONTENT
Supporting Information
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The control experiments, copies of HPLC spectral for racemic and enatiomerically enriched
compounds and NMR spectral for all new compounds. This information is available free of charge
via the Internet at http://pubs.acs.org.
Xꢀray data for compounds 4a and 7ka (CIF).
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AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: ghm@htu.edu.cn
*Eꢀmail: xiemingsheng@htu.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful for the financial support from the National Natural Science Foundation of China
(Nos. 21372066, 21472037, and 21402041), the National Basic Research Program of China (973
Program, No. 2014CB560713), the Plan for Scientific Innovation Talent of Henan Province
(164200510008), Henan Normal University National Outstanding Youth Cultivation Fund
(
14JR003), China Postdoctoral Science Foundation funded project (2016M592293), and Program
for Innovative Research Team in Science and Technology in University of Henan Province
15IRTSTHN003).
REFERENCES
1) (a) Trost, B. M. Chem. Rev. 1996, 96, 395. (b) Trost, B. M.; Crawley, M. L. Chem. Rev. 2003,
(
(
103, 2921. (c) Helmchen, G.; Pfaltz, A. Acc. Chem. Res. 2000, 33, 336. (d) Lu, Z.; Ma, S. Angew.
Chem., Int. Ed. 2008, 47, 258. (e) Hartwig, J. F.; Stanley, L. M. Acc. Chem. Res. 2010, 43, 1461. (f)
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1
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7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Liu, T.ꢀY.; Xie, M.; Chen, Y.ꢀC. Chem. Soc. Rev. 2012, 41, 4101.
(2) Examples for carbon nucleophiles see: (a) Huang, X.; Peng, J.; Dong, L.; Chen, Y.ꢀC. Chem.
Commun. 2012, 48, 2439. (b) Nishimine, T.; Taira, H.; Tokunaga, E.; Shiro, M.; Shibata, N. Angew.
Chem., Int. Ed. 2016, 55, 359. (c) Tong, G.; Zhu, B.; Lee. R.; Yang, W.; Tan, D.; Yang, C.; Han, Z.;
Yan, L.; Huang, K.ꢀW.; Jiang, Z. J. Org. Chem. 2013, 78, 5067, and the references cited therein.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(3) Examples for nitrogen nucleophiles see: (a) Cui, H.ꢀL.; Feng, X.; Peng, J.; Lei, J.; Jiang, K.;
Chen, Y.ꢀC. Angew. Chem., Int. Ed. 2009, 48, 5737. (b) Wang, X.; Guo, P.; Han, Z.; Wang, X.;
Wang, Z.; Ding, K. J. Am. Chem. Soc. 2014, 136, 405. (c) Huang, J.ꢀR.; Cui, H.ꢀL.; Lei, J.; Sun,
X.ꢀH.; Chen, Y.ꢀC. Chem. Commun. 2011, 47, 4784. (d) Ye, K.ꢀY.; Cheng, Q.; Zhuo, C.ꢀX.; Dai,
L.ꢀX.; You, S.ꢀL. Angew. Chem., Int. Ed. 2016, 55, 8113, and the references cited therein.
(4) Examples for phosphorus nucleophiles see: (a) Kalyva, M.; Zografos, A. L.; Kapourani, E.;
Giambazolias, E.; Devel, L.; Papakyriakou, A.; Dive, V.; Lazarou, Y. G.; Georgiadis, D. Chem. Eur.
J. 2015, 21, 3278. (b) Deng, H.ꢀP.; Shi, M. Eur. J. Org. Chem. 2012, 183. (c) Sun, W; Hong, L.;
Liu, C.; Wang, R. Org. Lett. 2010, 12, 3914.
(5) Examples for sulfur nucleophiles see: (a) Liu, X.ꢀW.; Han, W.ꢀY.; Liu, X.ꢀL.; Zhou, Y.; Zhang,
X.ꢀM.; Yuan, W.ꢀC. Tetrahedron 2014, 70, 9191. (b) Lin, A.; Mao, H.; Zhu, X.; Ge, H.; Tan, R.;
Zhu, C.; Cheng, Y. Adv. Synth. Catal. 2011, 353, 3301. (c) Xu, Q.ꢀL.; Dai, L.ꢀX.; You, S.ꢀL. Org.
Lett. 2010, 12, 800.
(6) Example for boron nucleophile see: Ramachandran, P. V.; Pratihar, D.; Biswas, D.; Srivastava,
A.; Reddy, M. V. R. Org. Lett. 2004, 6, 481.
(7) (a) Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 4545. (b) Kim, J. N.; Lee, .H. J.;
Gong, J. H. Tetrahedron Lett. 2002, 43, 9141. (c) Kimura, M.; Uozumi, Y. J. Org. Chem. 2007, 72,
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7
8
9
7
07.
(8) (a) Lam, F. L.; AuꢀYeung, T. T.ꢀL.; Kwong, F. Y.; Zhou, Z.; Wong, K. Y.; Chan, A. S. C. Angew.
Chem., Int. Ed. 2008, 47, 1280. (b) Kato, M.; Nakamura, T.; Ogata, K.; Fuzuzawa, S. Eur. J. Org.
Chem. 2009, 5232.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(
9) (a) Kim, H.; Lee, C. Org. Lett. 2002, 4, 4369. (b) Haight, A. R.; Stoner, E. J.; Peterson, M. J.;
Grover, V. K. J. Org. Chem. 2003, 68, 8092. (c) Kim, H.; Lee, C. Org. Lett. 2002, 4, 4369.
(
(
(
(
10) López, F.; Ohmura, T.; Hartwig, J. F. J. Am. Chem. Soc. 2003, 125, 3426.
11) Qu, J.; Roßberg, L.; Helmchen, G. J. Am. Chem. Soc. 2014, 136, 1272.
12) Hu, Z.ꢀK.; Cui, H.ꢀL.; Jiang, K; Chen, Y.ꢀC. Sci. China, Ser. B: Chem. 2009, 52, 1309.
13) Zhu, B.; Yan, L.; Pan, Y.; Lee, R.; Liu, H.; Han, Z.; Huang, K.ꢀW.; Tan, C.ꢀK.; Jiang, Z. J.
Org. Chem. 2011, 76, 6894.
14) (a) Han, Z.ꢀY.; Chen, D.ꢀF.; Wang, Y.ꢀY.; Guo, R.; Wang, P.ꢀS.; Wang, C.; Gong, L.ꢀZ. J. Am.
(
Chem. Soc. 2012, 134, 6532. (b) Shintani, R.; Maciver, E. E.; Tamakuni, F.; Hayashi, T. J. Am.
Chem. Soc. 2012, 134, 16955. (c) Lee, K.ꢀS.; Katsoulis, D.; Choi, J. ACS Catal. 2016, 6, 1493.
(15) Lyothier, I.; Defieber, C.; Carreira, E. M. Angew. Chem., Int. Ed. 2006, 45, 6204.
(
16) Ueno, S.; Hartwig, J. F. Angew. Chem., Int. Ed. 2008, 47, 1928.
(17) Ye, F.; Zheng, Z.ꢀJ.; Li, L.; Yang, K.ꢀF.; Xia, C.ꢀG.; Xu, L.ꢀW. Chem. Eur. J. 2103, 19, 15452.
18) Bellini, R.; Magra, M.; Biosca, M.; Norrby, P.ꢀO.; Pàmies, O.; Diéguez, M.; Moberg, C. ACS
Catal. 2016, 6, 1701.
19) (a) Kikukawa, Y.; Kuroda, Y.; Yamaguchi, K.; Mizuno, N. Angew. Chem., Int. Ed. 2012, 51,
2434. (b) John, J.; Gravel, E.; Hagège, A.; Li, H.; Gacoin, T.; Doris, E. Angew. Chem., Int. Ed.
(
(
2
011, 50, 7533. (c) Limnios, D.; Kokotos, C. G. ACS Catal. 2013, 3, 2239. (d) Kim, S. M.; Jeon,
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5
6
M.; Kim, K. W.; Park, J.; Lee, I. S. J. Am. Chem. Soc. 2013, 135, 15714.
(20) Ma, S.; Gao, W. J. Org. Chem. 2002, 67, 6104.
(21) (a) Zhang, S.ꢀJ.; Cui, H.ꢀL.; Jiang, K.; Li, R.; Ding, Z.ꢀY.; Chen, Y.ꢀC. Eur. J. Org. Chem.
0
1
2
3
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5
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7
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0
1
2
3
4
5
6
7
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0
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3
4
5
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3
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5
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7
8
9
0
2009, 5804. (b) Lian, X.; Guo, S.; Wang, G.; Lin, L.; Liu, X.; Feng, X. J. Org. Chem. 2014, 79,
7703.
(22) Baidya, M.; Remennikov, G. Y.; Mayer, P.; Mayr, H. Chem. Eur. J. 2010, 16, 1365.
(23) (a) Ogawa, S.; Shibata, N.; Inagaki, J.; Nakamura, S.; Toru, T.; Shiro, M. Angew. Chem., Int.
Ed. 2007, 119, 8820. (b) Furukawa, T.; Kawazoe, J.; Zhang, W.; Nishimine, T.; Tokunaga, E.;
Matsumoto, T.; Shiro, M.; Shibata, N. Angew. Chem., Int. Ed. 2011, 50, 9684.
(
24) Sawama, Y.; Masuda, M.; Yasukawa, N.; Nakatani, R.; Nishimura, S.; Shibata, K.; Yamada,
T.; Monguchi, Y.; Suzuka, H.; Takagi, Y.; Sajiki, H. J. Org. Chem. 2016, 81, 4190.
25) Yang, K.ꢀS.; Lee, W.ꢀD.; Pan, J.ꢀF.; Chen, K. J. Org. Chem. 2003, 68, 915.
(26) Iwabuchi, Y.; Naktani, M.; Yokoyama, N.; Hatakeyama, S. J. Am. Chem. Soc. 1999, 101,
0219.
(
1
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