Enantioselective desymmetrization of bicyclic hydrazines using a C 2-symmetric N-heterocyclic carbene (NHC) palladium complex as catalyst

Article abstract of DOI:10.1021/om4010687

The first example of palladium-catalyzed enantioselective desymmetrization of 2,3-bicyclic hydrazines with arylboronic acids through a ring-opening process is described by using a chiral C₂-symmetric N-heterocyclic carbene (NHC) palladium complex as the catalyst. The reaction can be performed under convenient conditions to give trans-1,2-disubstituted 3-cyclopentenes 3 with high regioselectivity in good to excellent yields (up to 95%) and moderate to good enantioselectivities (up to 88% ee).

Full text of DOI:10.1021/om4010687

Article
pubs.acs.org/Organometallics
Enantioselective Desymmetrization of Bicyclic Hydrazines using a
C2‑Symmetric N‑Heterocyclic Carbene (NHC) Palladium Complex as
Catalyst
Peng Gu,† Qin Xu,*,† and Min Shi*,†,‡
†Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China
University of Science and Technology, 130 Mei-Long Road, Shanghai 200237, People’s Republic of China
‡State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354
Fenglin Road, Shanghai 200032, People’s Republic of China
S
* Supporting Information
ABSTRACT: The first example of palladium-catalyzed
enantioselective desymmetrization of 2,3-bicyclic hydrazines
with arylboronic acids through a ring-opening process is
described by using a chiral C2-symmetric N-heterocyclic
carbene (NHC) palladium complex as the catalyst. The
reaction can be performed under convenient conditions to give
trans-1,2-disubstituted 3-cyclopentenes 3 with high regiose-
lectivity in good to excellent yields (up to 95%) and moderate
to good enantioselectivities (up to 88% ee).
centered nucleophiles in the presence of palladium complexes,
affording substituted cyclopentenes and polycyclic compounds
in good yields.6
INTRODUCTION
■
Transition-metal-catalyzed annulation processes have recently
attracted much interest as efficient strategies for the
construction of functional molecular frameworks in organic
synthesis.1 Among the diverse transition metals, palladium,
rhodium, nickel, and copper were found to be effective catalysts
in the hetero- and carboannulation of unsaturated cycloalkanes,
dienes, and alkynes, giving a wide variety of arene-containing
heterocycles and carbocycles in good yields under mild
conditions.2 Aza bicyclic alkenes, which could be prepared by
simple Diels−Alder cycloadditions between cyclopentadiene
and diazo compounds,3 exhibit great synthetic potential. The
existence of a strained carbon−carbon double bond and N−N
bond in symmetrical bicyclic hydrazines allows them to be
easily activated by the metal catalysts. The regular modes of
transition-metal-activated bicyclic hydrazines are shown in
Scheme 1.
The reactivity of aza bicyclic alkenes has been studied with
various nucleophiles under transition-metal-catalyzed condi-
tions, leading to the formation of highly stereoselective
disubstituted cyclopentenes.4 Palladium complexes, which
were found to be efficient transition-metal catalysts, have
been applied in the reaction of aza bicyclic alkenes since 2001.
For example, Kaufmann and co-workers reported the
palladium-catalyzed stereoselective ring opening of bicyclic
hydrazine with aryl iodides to afford the corresponding
cyclopentenes and hydroarylated adducts in good yields.5
Then, Radhakrishnan and co-workers disclosed a series of the
desymmetrization of bicyclic hydrazine with mono- or bis-
Enantioselective desymmetrization of aza bicyclic alkenes
with organoboronic acids has been considered an efficient way
of generating chiral building blocks which have biological
activities, such as a central nervous system (CNS) stimulant
agent (Scheme 1).7 In this respect, Pineschi and co-workers
reported the first example of chiral Rh-catalyzed asymmetric
ring opening of bicyclic hydrazine with arylboronic acids, giving
the adducts in moderate enantioselectivities (12−89% ee).8
Then, Lautens and co-workers reported the same reactions
catalyzed by a series of chiral Rh phosphine complexes to give
the desired products in excellent ee values (up to 99% ee).9
Different kinds of chiral products 3 and 4 could be obtained by
choosing different chiral phosphine ligands. However, to the
best of our knowledge, the palladium-catalyzed asymmetric ring
opening of bicyclic hydrazine with arylboronic acids still
remains unexplored. Only one example of palladium-catalyzed
enantioselective desymmetrization of aza bicyclic alkenes with
other nucleophiles such as phenols has been reported to give
the ring-opened products with moderate enantioselectivities
(up to 58% ee).10 Herein, we report an efficient chiral NHC−
Pd-catalyzed enantioselective desymmetrization of aza bicyclic
alkenes with arylboronic acids, affording the desired adducts in
Received: November 1, 2013
Published: December 4, 2013
© 2013 American Chemical Society
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Scheme 1. Activation Modes of Bicyclic Hydrazines by Transition Metals
1H NMR spectroscopic data of the crude product mixture.
Then several other bases were screened, and the results of these
experiments are summarized in Table 1 (entries 1−6). It was
found that when LiOH·H2O was used as the base, the major
product 3aa was isolated in the highest product ratio of 15/1
along with the highest ee value of 78% (Table 1, entry 2). We
assumed that the reactivity and selectivity of diaza bicycle 1a
were enhanced due to the activation of dicarbonyl groups by
lithium ion when LiOH·H2O was used as the base.12 Other
organic solvents, such as 1,4-dioxane and toluene, have also
been used for this reaction (Table 1, entries 7 and 8). In 1,4-
dioxane, only the ring-opened product 3aa was formed along
with a slightly decreased enantioselectivity of 68% ee.
Tetrahydrofuran (THF) was the best solvent for this reaction.
Examination of the temperature revealed that carrying out the
reaction at 25 °C gave the ring-opened product 3aa as the sole
product in 95% yield along with an 88% ee value (Table 1,
entry 10), in which the same adduct was obtained with 68% ee
in the previous literature.9a,b The absolute configuration of the
product 3aa was assigned as 1R,2S, which was confirmed by
comparison of the specific rotation and the HPLC trace with
those in the previous literature.9a,b
good yields along with moderate to good enantioselectivities
(up to 88% ee).
RESULTS AND DISCUSSION
■
Initially, we utilized the diaza bicycle 1a (1.0 equiv) and
phenylboronic acid (2.0 equiv) as substrates using K2CO3 (1.0
equiv) as a base with the NHC−Pd(OAc)2 complex C1 (5 mol
%) (Figure 1) as the catalyst to examine the reaction
Figure 1. Chiral NHC−Pd(OAc)2 complex C1.
outcome.11 The ring-opened product 3aa was obtained in
85% yield with 64% ee value at 50 °C in a THF and water (10/
1) solvent mixture. The arylation adduct 4aa was also isolated,
and the ratio of products 3aa and 4aa was confirmed as 8/1 by
Having established the optimal catalytic conditions, a variety
of diaza bicycles 1 having diverse substituents on the ester
groups were evaluated for reactions with phenylboronic acid
Table 1. Optimization of the Reaction Conditions for Enantioselective Desymmetrization of Diaza Bicycles with Phenylboronic
Acids
a
b
c
d
entry
base
T (°C)
50
t (h)
solvent
3aa/4aa
yield of 3aa (%)
ee of 3aa (%)
1
2
3
4
5
6
7
8
9
10
K2CO3
36
36
THF
8/1
85
83
82
46
64
42
88
n.r.
65
95
64
78
68
64
44
56
68
LiOH·H2O
KOH
50
THF
15/1
6/1
50
36
THF
KF
50
72
THF
7/1
Et3N
50
72
THF
6/1
NaOAc
50
100
36
THF
4/1
LiOH·H2O
LiOH·H2O
LiOH·H2O
LiOH·H2O
50
dioxane
toluene
THF
100/0
50
72
80
36
9/1
78
88
room temp
36
THF
100/0
a
Reaction conditions: NHC−Pd catalyst (5 mol %), alkene (0.1 mmol), phenylboronic acid (0.2 mmol), and base (0.1 mmol); reaction carried out
b
c
d
in solvent/water (10/1). Determined by 1H NMR spectra. Yield of isolated product 3aa. Enantiomeric excess of product 3aa was determined by
chiral HPLC.
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under the optimal conditions. The isopropyl carboxylate
protected product 3ba was produced in 89% yield and 82%
ee (Table 2, entry 1). The less sterically hindered Cbz group
with diaza bicycle 1a under the optimal conditions. We found
that the corresponding ring-opened products were obtained in
good yields and moderate to good enantioselectivities (ee
values up to 86%), depending on the electronic effect and steric
bulkiness of the employed arylboronic acids. As for ortho-
substituted arylboronic acids, the electron-deficient species
generally led to high enantioselectivities (Table 2, entries 4 and
5), but electron-rich and more sterically hindered substrates
showed poor reactivities and the reactions should be carried out
at 50 °C, affording the ring-opened products 3ad and 3ae in
80% and 76% yields along with lower enantioselectivities,
respectively (Table 2, entries 6 and 7). Under the same
conditions, 2-methoxyphenylboronic acid gave the desired ring-
opened product 3af in a trace amount (Table 2, entry 8). In
comparison, Lautens’s Rh phosphine complexes showed higher
catalytic activities when these 2-substituted arylboronic acids
were used as substrates, affording the corresponding ring-
opened products with excellent enantioselectivities. In the cases
of para-substituted arylboronic acids, the electron-rich species
gave the desired adduct in higher enantioselectivity: 86% ee
(Table 2, entries 9 and 10).
The proposed mechanism for the reaction is illustrated in
Scheme 2 on the basis of the related literature and our previous
works.11a,13 Initially, the NHC−Pd(OAc)2 complex C1 is
transformed into the corresponding Pd hydroxo complex A in
the presence of base and water. Transmetalation with
arylboronic acid gives rise to the palladium aryl complex B,
which can coordinate to alkene 1. The subsequent
carbopalladation is presumed to be irreversible, leading to the
formation of complex C with the activation of dicarbonyl
groups by lithium ion. The complex C can directly produce the
arylation product 4 through a protodemetalation process or can
give the ring-opened product 3 via a β-nitrogen elimination and
subsequent protodemetalation process.
Table 2. Enantioselective Ring Opening of Diaza Bicycles
with Substituted Arylboronic Acids
a
b
c
entry
R
Ar
yield (%)
ee (%)
1
2
3
4
5
i-Pr (1b)
Bn (1c)
C6H5 (2a)
89 (3ba)
92 (3ca)
95 (3da)
62 (3ab)
75 (3ac)
80 (3ad)
76 (3ae)
82
82
73
64
86
36
39
C6H5 (2a)
Et (1d)
C6H5 (2a)
t-Bu (1a)
t-Bu (1a)
t-Bu (1a)
t-Bu (1a)
t-Bu (1a)
t-Bu (1a)
t-Bu (1a)
2-FC6H4 (2b)
2-CIC6H4/2c
1-naphthalene (2d)
2-MeC6H4 (2e)
2-MeOC6H4 (2f)
4-MeC6H4 (2g)
4-FC6H4 (2h)
d
6
d
7
d
8
trace (3af)
72 (3ag)
68 (3ah)
9
86
45
10
a
Reaction conditions: NHC−Pd catalyst (5 mol %), alkene (0.1
mmol), arylboronic acid (0.2 mmol) and LiOH-H20 (0.1 mmol);
reaction carried out in THF/water (10/1) at room temperature for 72
h. Yield of isolated product 3. Enantiomeric excess of product 3 was
b
c
d
determined by chiral HPLC. The reaction was carried out at 50 °C.
substituted product 3ca and ethyl carboxylate protected
product 3da were both obtained in excellent yields and good
enantioselectivities as 82% and 73% ee, respectively (Table 2,
entries 2 and 3). The slight decrease in enantioselectivity
suggests that the steric hindrance of the N-protecting groups
has a direct impact on the chiral induction. Encouraged by the
above results, we next utilized various arylboronic acids to react
In conclusion, we have successfully developed an efficient
catalytic system for the enantioselective desymmetrization of
Scheme 2. Plausible Reaction Mechanism
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(CHIRALPACK OD-H, hexane/iPrOH 90/10, 0.5 mL/min, 215 nm):
diaza bicycles with arylboronic acids catalyzed by the chiral C2-
symmetric NHC−Pd(OAc)2 complex C1 under mild con-
ditions. The potential biologically relevant (1R,2S)-1-amine-2-
arylcyclopentenes 3 can be obtained in good to excellent yields
(up to 95%) and moderate to good enantioselectivities (up to
88% ee). Using LiOH·H2O as the base can significantly
improve the catalytic efficiency. We assume that the activation
of two carbonyl groups in diaza bicycles by the lithium ion plays
an important role in the reaction.
20
tmajor = 16.9 min, tminor = 14.7 min. [α]D = −236.1 (c = 1.02,
1
CH2Cl2). H NMR (400 MHz, CDCl3, TMS): δ 7.29−7.21 (m, 5H),
6.57 (br, 1H), 5.86 (br, 1H), 5.71 (br, 1H), 4.76 (br, 1H), 4.25−4.19
(m, 2H), 4.01 (br, 3H), 2.72−2.47 (br m, 2H), 1.29−1.25 (m, 3H),
1.14−0.96 (m, 3H).
Di-tert-butyl (1R,2S)-N,N′-(2-(2′-Fluorophenyl)cyclopent-3-enyl)-
hydrazinedicarboxylate (3ab). 3ab is a known compound;9a 62%
yield (24.3 mg). The ee value was 64%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 90/10, 0.8 mL/min, 225 nm):
tmajor = 24.3 min, tminor = 15.7 min. [α]D20 = −49.7 (c = 1.23, CH2Cl2).
1H NMR (400 MHz, CDCl3, TMS): δ 7.24−7.16 (m, 2H), 7.10 (t, J =
EXPERIMENTAL SECTION
■
7.6 Hz, 1H), 6.99 (t, J = 9.2 Hz, 1H), 6.31 and 6.10 (coalescing br,
1H), 5.91−5.90 (br m, 1H), 5.66 (br, 1H), 4.75 (br, 1H), 4.27 (br,
1H), 2.27−2.60 (br m, 2H), 1.49−1.19 (br m, 18H).
General Remarks. Optical rotations were determined in a solution
of CH2Cl2 at 20 °C; [α]D values are given in units of 10−1 deg cm2 g−1.
NMR spectra were recorded with a 400 MHz spectrometer in CDCl3.
Chemical shifts are reported in ppm downfield from internal TMS.
Mass spectra and HRMS were with a mass spectrometer. All reactions
were monitored by TLC. Flash column chromatography was carried
out using 300−400 mesh silica gel at increased pressure. All reactions
were performed under argon using standard Schlenk techniques. The
optical purities of products were determined by HPLC analysis with
chiral columns (Chiralpak AD-H and OD-H columns, 4.6 × 250 mm).
The NHC−Pd complex C1 was prepared according to the previously
reported procedure.11a The aza bicycles 1a−d were prepared by
literature procedures.9a,b The corresponding racemic products were
prepared according to the reported procedure.6b
Di-tert-butyl (1R,2S)-N,N′-(2-(2′-Chlorophenyl)cyclopent-3-enyl)-
9b
hydrazinedicarboxylate (3ac). 3ac is a known compound;
75%
yield (30.7 mg). The ee value was 86%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 90/10, 0.8 mL/min, 225 nm):
tmajor = 16.6 min, tminor = 12.5 min. [α]D20 = −72.4 (c = 2.24, CH2Cl2).
1H NMR (400 MHz, CDCl3, TMS): δ 7.31 (d, J = 7.2 Hz, 1H), 7.27−
7.22 (m, 2H), 7.16 (m, 1H), 6.34 and 6.16 (coalescing br, 1H), 5.93−
5.92 (br m, 1H), 5.60 (br, 1H), 4.81−4.69 (br m, 1H), 4.43 (br, 1H),
2.73−2.62 (m, 2H), 1.49−1.12 (m, 18H).
Di-tert-butyl (1R,2S)-N,N′-(2-(1′-Naphthyl)cyclopent-3-enyl)-
hydrazinedicarboxylate (3ad). 3ad is a known compound;9a 80%
yield (34.0 mg). The ee value was 36%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 80/20, 0.5 mL/min, 215 nm):
tmajor = 19.9 min, tminor = 14.9 min. [α]D20 = −26.0 (c = 2.11, CH2Cl2).
1H NMR (400 MHz, CDCl3, TMS): δ 8.20 (br, 1H), 7.85 (d, J = 7.6
Note: NMR analysis displayed very broad peaks for all ring-opened
products 3 due to rotamers of the bis-carbamate hydrazine moiety.
1
The resolution for both H and 13C NMR spectroscopic data did not
improve significantly when the temperature was varied.
Typical Procedure of the NHC−Palladium-Catalyzed Enan-
tioselective Desymmetrization of Diaza Bicycles with Arylbor-
onic Acids. NHC−Pd(OAc)2 complex C1 (5 μmol, 0.05 equiv), diaza
bicycle 1 (0.1 mmol, 1.0 equiv), arylboronic acid (0.2 mmol, 2.0
equiv), and LiOH·H2O (0.1 mmol, 1.0 equiv) were placed in a tube
under argon, and the mixed solvent of tetrahydrofuran and water (10/
1) was added in the tube through a syringe. The mixture was stirred at
room temperature for 72 h. After the reaction was complete, the
solvent was removed under reduced pressure. The residue was purified
by flash column chromatography on a silica gel column (5−10%
EtOAc/petroleum ether as an eluent) to give the desired ring-opened
products 3.
Hz, 1H), 7.73 (d, J = 7.6 Hz, 1H), 7.50−7.34 (m, 4H), 6.40 (br, 1H),
5.96 (br, 1H), 5.83 (br, 1H), 4.89−4.72 (br m, 2H), 2.81−2.60 (m,
2H), 1.49−1.26 (br m, 18H).
Di-tert-butyl (1R,2S)-N,N′-(2-(2′-Methylphenyl)cyclopent-3-enyl)-
hydrazinedicarboxylate (3ae). 3ae is a known compound;9a 76%
yield (29.5 mg). The ee value was 39%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 98/2, 0.8 mL/min, 220 nm):
tmajor = 56.4 min, tminor = 72.3 min. [α]D20 = −40.1 (c = 2.59, CH2Cl2).
1H NMR (400 MHz, CDCl3, TMS): δ 7.19−7.05 (m, 4H), 6.21 and
6.06 (coalescing br, 1H), 5.90−5.85 (m, 1H), 5.64 (br, 1H), 4.75 (br,
1H), 4.18 (br, 1H), 2.80−2.52 (m, 2H), 2.34 (s, 3H), 1.58−1.10 (br
m, 18H).
Di-tert-butyl (1R,2S)-N,N′-(2-Phenylcyclopent-3-enyl)-
hydrazinedicarboxylate (3aa). 3aa is a known compound;9a 95%
yield (35.2 mg). The ee value was 88%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 98/2, 0.8 mL/min, 225 nm):
Di-tert-butyl (1R,2S)-N,N′-(2-(4′-Methylphenyl)cyclopent-3-enyl)-
hydrazinedicarboxylate (3ag). 3ag is a colorless oil; 72% yield (28.0
mg). The ee value was 86%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 90/10, 0.5 mL/min, 214
20
tmajor = 79.9 min, tminor = 89.2 min. [α]D = −172.1 (c = 1.59,
1
20
CH2Cl2). H NMR (400 MHz, CDCl3, TMS): δ 7.37−7.19 (m, 5H),
nm): tmajor = 28.4 min, tminor = 25.5 min. [α]D = −76.5 (c = 1.70,
1
6.26 (br, 1H), 5.87−5.85 (m, 1H), 5.70 (br m, 1H), 4.70 (br, 1H),
3.94 (br, 1H), 2.74−2.58 (br m, 2H), 1.49−1.11 (br m, 18H).
Diisopropyl (1R,2S)-N,N′-(2-Phenylcyclopent-3-enyl)-
hydrazinedicarboxylate (3ba). 3ba is a known compound;6b 89%
yield (30.7 mg). The ee value was 82%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 90/10, 0.5 mL/min, 215 nm):
CH2Cl2). H NMR (400 MHz, CDCl3, TMS): δ 7.20−7.05 (m, 4H),
6.26 (br, 1H), 5.89−5.80 (br m, 1H), 5.68 (br, 1H), 4.67 (br, 1H),
3.90 (br, 1H), 2.71−2.45 (m, 2H), 2.31 (s, 3H), 1.52−1.20 (br m,
18H). 13C NMR (100 MHz, CDCl3): δ 155.8, 154.8, 140.5, 135.9,
132.9, 129.7, 129.1, 127.4, 81.1 (2), 67.8 (br, rotamers), 53.4, 35.2,
28.1 (3), 28.0 (3), 21.0. MS (ESI): m/z 411.2 (M+ + Na, 100). HRMS
(ESI): calcd for C22H32N2O4Na, 411.2260; found, 411.2254.
20
tmajor = 23.2 min, tminor = 18.0 min. [α]D = −147.5 (c = 1.40,
1
CH2Cl2). H NMR (400 MHz, CDCl3, TMS): δ 7.31−7.19 (m, 5H),
Di-tert-butyl (1R,2S)-N,N′-(2-(4′-Fluorophenyl)cyclopent-3-enyl)-
hydrazinedicarboxylate (3ah). 3ah is a colorless oil; 68% yield (26.7
mg). The ee value was 45%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 95/5, 0.8 mL/min, 225
6.39 (br, 1H), 5.87−5.85 (m, 1H), 5.71−5.70 (m, 1H), 5.03−4.95 (m,
1H), 4.77 (br, 2H), 3.99 (br, 1H), 2.71−2.59 (br m, 2H), 1.30−1.13
(br m, 12H).
Dibenzyl (1R,2S)-N,N′-(2-Phenylcyclopent-3-enyl)-
hydrazinedicarboxylate (3ca). 3ca is a known compound;9b 92%
yield (40.5 mg). The ee value was 82%, as determined by chiral HPLC
(CHIRALPACK AD-H, hexane/iPrOH 90/10, 0.5 mL/min, 215 nm):
20
nm): tmajor = 29.9 min, tminor = 34.6 min. [α]D = −63.1 (c = 2.31,
1
CH2Cl2). H NMR (400 MHz, CDCl3, TMS): δ 7.23 (br, 2H), 6.98
(t, J = 8.8 Hz, 2H), 6.26 (br, 1H), 5.90−5.82 (m, 1H), 5.67 (br, 1H),
4.66 (br, 1H), 4.17−3.38 (m, 1H), 2.73−2.43 (m, 2H), 1.58−1.07 (br
m, 18H). 19F NMR (376 MHz, CDCl3, CFCl3): δ −116.72 and
−117.17 (coalescing br). 13C NMR (100 MHz, CDCl3): δ 161.7 (d, J
= 242 Hz), 155.9, 154.8, 139.4, 132.5, 130.1, 129.0 (d, J = 6.6 Hz),
115.1 (d, J = 21.2 Hz), 81.3 (2), 68.2 and 66.0 (br, rotamers), 53.0,
35.0, 28.1 (3), 27.9 (3). MS (ESI): m/z 415.2 (M+ + Na, 100). HRMS
(ESI): calcd for C21H29N2O4FNa, 415.2004; found, 415.2009.
20
tmajor = 52.8 min, tminor = 39.5 min. [α]D = −111.7 (c = 1.59,
CH2Cl2). 1H NMR (400 MHz, CDCl3, TMS): δ 7.25−6.68 (m, 15H),
6.69 (br, 1H), 5.75 (br, 1H), 5.61 (br, 1H), 5.10 (br, 2H), 4.91 (br,
2H), 4.72 (br, 1H), 3.93 (br, 1H), 2.58−2.43 (br m, 2H).
Diethyl (1R,2S)-N,N′-(2-Phenylcyclopent-3-enyl)-
hydrazinedicarboxylate (3da). 3da is a known compound;9a 95%
yield (30.1 mg). The ee value was 73%, as determined by chiral HPLC
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ASSOCIATED CONTENT
■
S
* Supporting Information
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5, 4771−4774.
Figures giving NMR spectra and chiral HPLC traces of the
compounds shown in Tables 1 and 2. This material is available
free of charge via the Internet at http://pubs.acs.org.
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(b) Wang, W. F.; Zhang, T.; Shi, M. Organometallics 2010, 29, 928−
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AUTHOR INFORMATION
■
Corresponding Author
*M.S.: e-mail, Mshi@mail.sioc.ac.cn; fax, 86-21-64166128.
(13) (a) Lautens, M.; Hiebert, S.; Renaud, J. L. J. Am. Chem. Soc.
2001, 123, 6834−6839. (b) Lautens, M.; Dockendorff, C.; Fagnou, K.;
Malicki, A. Org. Lett. 2002, 4, 1311−1314. (c) Lautens, M.;
Dockendorff, C. Org. Lett. 2003, 5, 3695−3698.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the Shanghai Municipal Committee of Science and
Technology (11JC1402600), the National Basic Research
Program of China ((973)-2010CB833302), the Fundamental
Research Funds for the Central Universities, and the National
Natural Science Foundation of China for financial support
(21072206, 20472096, 21372241, 20672127, 21102166,
21121062, 21302203, 21361140350, and 20732008).
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