Highly stereoselective olefin cyclopropanation of diazooxindoles catalyzed by a C2-symmetric spiroketal bisphosphine/Au(I) complex

Article abstract of DOI:10.1021/ja4040895

A spiroketal bisphosphine (SKP) derived chiral digold complex is identified as a powerful catalyst for the highly diastereo- and enantioselective synthesis of spirocyclopropyloxindoles from diazooxindoles and a broad range of alkenes, including both cis and trans 1,2-disubstituted alkenes.

Full text of DOI:10.1021/ja4040895

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Highly Stereoselective Olefin Cyclopropanation of Diazooxindoles
Catalyzed by a C2-Symmetric Spiroketal Bisphosphine/Au(I) Complex
Zhong-Yan Cao, Xiaoming Wang, Chen Tan, Xiao-Li Zhao, Jian Zhou, and Kuiling Ding
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja4040895 • Publication Date (Web): 22 May 2013
Downloaded from http://pubs.acs.org on May 23, 2013
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Highly Stereoselective Olefin Cyclopropanation of Diazooxindoles
Catalyzed by a C2-Symmetric Spiroketal Bisphosphine/Au(I) Complex
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Zhong-Yan Cao,† Xiaoming Wang,‡ Chen Tan,† Xiao-Li Zhao,† Jian Zhou*,† and Kuiling Ding‡
†Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China
Normal University, 3663N Zhongshan Road, Shanghai 200062 China;
‡State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy
of Sciences, 345 Lingling Road, Shanghai 200032, China
Supporting Information Placeholder
wards alkenes.8a To meet this challenge, Arai and our
group independently reported the first example of asym-
ABSTRACT: A spiroketal bisphosphine (SKP) derived
chiral digold complex is identified as a powerful catalyst
for the highly diastereo- and enantioselective synthesis
of spirocyclopropyloxindoles from diazooxindoles and a
broad range of alkenes, including both cis and trans 1,2-
disubstituted alkenes.
metric cyclopropanation of olefins with diazooxindole 1 by
13
using either Rh2(S-PTTL)4 or (R)-difluorphos/Hg(II)11a
complex as the catalyst, respectively. Although up to 99%
ee has been achieved for cyclopropanation of styrenes by
mercury catalysis, the 1,2-disubstituted alkenes proved to
be difficult substrates in terms of the enantioselectivity
(Scheme 1). On the other hand, Au(I), isoelectronic with
Hg(II), has been shown effective in the catalysis of olefin
Since the pioneering work of Nozaki and Noyori,1a the
cyclopropanation with diazo reagents,15 but a highly
metal-catalyzed olefin cyclopropanation using diazo com-
enantioselective version has not yet been reported so far to
pounds has been established as a powerful strategy to
our knowledge. Inspired by the leading work of Toste16
access optically active cyclopropanes.2 Despite significant
and Davies17 on the exploration of Au(I)-carbenoids in
achievements,3-6 it is still highly desirable to develop effi-
asymmetric catalysis, we thus turned to examine the po-
cient synthesis of 1,2,3-trisubstituted cyclopropanes from
tential of chiral gold catalysis in the cyclopropanation of
both trans and cis 1,2-disubstituted alkenes with full
the challenging olefins, as Au(I) has been demonstrated to
control of stereoselectivity.7 In this context, a successful
be superior to Hg(II) in many reactions.14
protocol involving the acceptor-substituted diazoacetates
Ar
H
N2
has been recently developed by Sun and Tang using a
chiral BOX/CuI catalyst.7g By contrast, the corresponding
process using donor-acceptor diazo compounds remains a
challenge, since donor/acceptor substituted carbenoids
are known to be much more sensitive to the steric features
of olefinic substrates than acceptor-only ones.7e Especially,
electronically unbiased trans-1,2-disubstituted alkenes
proved to be difficult substrates for cyclopropanation, as
revealed by Davies’ systematic studies on the Rh-catalyzed
reactions of aryldiazoacetates with electron-rich trans-
anethole (cyclopropanated in up to 87% ee) or electron-
neutral trans-β-methyl styrene (only C-H insertion prod-
uct).7e Herein, we wish to report a highly stereoselective
cyclopropanation of cyclic donor-acceptor diazooxindoles
with various types of alkenes, including both cis and trans
1,2-disubstituted alkenes, catalyzed by a novel dinuclear
Au(I) complex derived from chiral SKP L1.
Ar
H
R'
R'
R'
2
cat.
R
+
R
O
or
N
O
H
Ar
N
1
4 or 6
3
H
This work:
Previous work (ref 11a):
O
F
F
O
O
PPh2
PPh2
O
PPh2 Ph2P
(S,S,S)-SKP L1/Au(I)
O
F
F
O
(R)-difluorphos/Hg(PF6)2
(12 example for 2, 45-95%, 81-95% ee)
(12 exmaple for 3, 48-88%, 88-94% ee)
(1 example for 2, 65%, 64% ee)
(1 example for 3, 50%, 60% ee)
Scheme 1. Mercury catalysis vs gold catalysis in the ole-
fin cyclopropanation with diazooxindoles
Indeed, an initial test proved that Au(I) catalyst was
much more reactive than a variety of metal catalysts we
tried in the olefin cyclopropanation of diazooxindole 1a
(Tables S1 and S2, supporting information, SI). This result
prompted us to further develop its asymmetric version by
screening various chiral phosphine ligands, and fortunate-
ly, SKP L1,18 was identified to be optimal in terms of reac-
tivity and stereoselectivity (Tables S3-5 in SI). Under the
The diazooxindole 1 is a versatile synthon for the 3,3-
disubstituted oxindoles,8 a type of privileged scaffolds in
natural products and drugs.9 Particularly, spirocyclopropyl
oxindoles are useful building blocks10,11a and interesting
targets in medicinal research,12 but the synthesis of which
via asymmetric olefin cyclopropanation using 1 was rarely
explored, probably due to its relatively low reactivity to-
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optimized reaction conditions, the complete conversion of
1a was observed within 0.3 h at 0 C in PhF in the pres-
the desired products 4j-l in good yields and excellent
diastereo- and enantioselectivities.
5
6
7
8
o
ence of 4.4 mol % of L1, 8.8 mol % of (Me2S)AuCl and 4.0
mol % of AgBF4, affording 4a in 90% yield, with excellent
dr and 90% ee (entry 1, Table 1). The dr value was deter-
Table 2. SKP L1/Au(I) Catalyzed Cyclopropanation of
cis-1,2-Disubstituted Alkenes 2a,b
9
1
N2
mined by H NMR analysis of an aliquot taken from the
R
R2
L1(AuCl)2 (4.4 mol %)
AgBF4 (4 mol %)
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R1
crude reaction mixture. A variety of SKP ligands (S,S,S)-
L2-6 were further examined, but proved to be less effec-
tive than L1 (entries 2-6 vs 1). With the ratio of 1a and 2a
varying from 1.0:5.0 to 1.2:1.0, the ee of product 4a was
improved to 94% (entry 7). The relative and absolute
configuration of product 4a was assigned by the X-ray
analysis of its sulfamide derivative 5. It should be noted
that no reaction took place at all in the absence of AgBF4,
and the amount of AgBF4 obviously influenced the level of
enantioselectivity. The best result was obtained with the
Ag/Au ratio of 1:2, and erosion of enantioselectivity was
observed when the ratio was over 1:2 (Table S4 in SI).
O
H
R
+
R1
R2
N
H
O
PhF, 0 o
(dr > 20:1)
C
H
2 (1.0 mmol)
N
1 (0.20 mmol)
4
H
R'
1a: R = H,
1b: R = 5-F
1c: R = 5-Cl
1d: R = 5-Me
Ph
2a: R' = H, 2b: R' = 4-Br
2c: R' = 5-Br, 2d: R' = 6-Br
2g
2e
2f
Br
Br
Br
H
H
H
O
N
H
H
O
H
H
O
H
O
N
N
N
H
H
4ac
4bc
4dc
H
4c
H
Table 1. Condition Optimization
0.2 h, 76%, 94% ee
0.2 h, 72%, 91% ee 0.3 h, 69%, 91% ee
0.2 h, 73%, 85% ee
N2
(S,S,S)-L (4.4 mol %)
(Me2S)AuCl (8.8 mol %)
H
O
*
Me
+
H
H
H
O
N
H
AgBF4 (4.0 mol %)
PhF, 0 o
*
H
Me
N
F
H
O
H
O
H
O
H
C
O
1a (0.2 mmol) 2a (1.0 mmol)
N
N
N
4h
H
N
4e
4f
4g
H
4a
H
H
H
L1: Ar = Ph
0.1 h, 88%, 92% ee
1.5 h, 95%, 93% ee
3 h, 45%, 90% ee
3 h, 60%, 82% ee
L2: Ar = -MeC H
o
6
4
L3: Ar = 3,5-Me2C6H3
L4: Ar = p-MeC6H4
L5: Ar = p-MeOC6H4
L6: Ar = p-FC6H4
Me
Ph
Me
Ph
Me
Ph
O
O
H
H
H
*
Me
H
H
H
F
Cl
*
Me
(S,S,S)-L
PAr2 Ar2P
H
O
O
N
O
N
O
N
N
4i
4j
H
4k
4l
H
H
yield
ee (%)b
H
time (h)
dr
(%)a
90
0.5 h, 63%, 82% ee
entry
L
0.1 h, 80%, 94% ee
0.5 h, 90%, 95% ee
0.5 h, 95%, 94% ee
0.3
1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
90
74
84
87
86
54
94
1
2
L1
L2
L3
L4
L5
L6
L1
c
a Isolated yield. b Determined by chiral HPLC analysis. 0.24
72
mmol 1 and 0.2 mmol 2 were used.
0.3
0.5
0.3
0.2
0.3
79
3
To our delight, the scope of olefins could be extended
to trans-1,2-disubstituted alkenes as well, as shown in
Table 3. It is noteworthy that electron-neutral alkene 3a,
without the activation by a donating group, reacted with
diazooxindole 1b-c smoothly and selectively to give the
desired cyclopropanes 6a-b in high yields with up to 90%
ee, without C-H insertion products being detected by GC-
MS or LC-MS analysis of the crude reaction mixture (en-
tries 1-2). As expected, trans-anethole 3b also reacted
smoothly with diazooxindoles to give cyclopropanes 6c-h
in good yields and excellent ee values (entries 3-8). The
high efficiency of the SKP L1/Au(I) was further exhibited
by a 4.0 mmol scale reaction of 1h and 3b with only 1.1
mol % of L1(AuCl)2 and 1.0 mol % of AgBF4, which gave
product 6g in 71% yield with 92% ee (entry 9). Alkene 3c,
with a methoxy group at the allylic position, selectively
gave the desired cyclopropanes 6i-j in good yields and
excellent ees (entries 10-11). The relative and absolute
configuration of product 6c was unambiguously deter-
mined by the X-ray analysis of its derivative 7, and those
of other products were tentatively assigned by analogy.
79
4
90
5
80
6
7c
76
aIsolated yield. bDetermined by HPLC analysis. c0.24 mmol 1a
and 0.2 mmol 2a were used.
The substrate scope of this protocol was first evaluated
in the reactions of various cis-alkenes 2a-g with
diazooxindoles 1a-d, by using 4.4 mol % of the catalyst
precursor L1(AuCl)2, prepared from L1 and (Me2S)AuCl,
and 4.0 mol % of AgBF4 (Table 2). Both substituted
indenes 2a-d and 1,2-dihydronaphthalene 2e worked well
with diazooxindole 1 to give polycyclic oxindoles 4a-g in
excellent dr and high to excellent ee. cis-Trisubstituted
alkene 2f also furnished products 4h-i, with two adjacent
quaternary centers, in excellent dr with up to 82% ee.
Acyclic cis alkene 2g was a viable substrate as well, giving
The SKP L1/Au(I) catalyst also allowed highly
stereoselective cyclopropanation of diazooxindole 1 with
monosubstituted or 1,1-disubstituted alkenes (Table 4).
Styrene derivatives afforded the desired products 9a-e in
excellent yield and ee. 1-Hexene reacted with 1b to give
product 9f with 70% ee, albeit in a modest yield (18%).
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When α-methylstyrene was used, the construction of con-
tinuous quaternary stereogenic centers was achieved to
afford products 9g-h in excellent dr and up to 93% ee.
5
6
7
8
Table 4. SKP L1/Au(I) Catalyzed Cyclopropanation of
Terminal and 1,1-Disubstituted Alkenes 8a,b
R4
R5
O
N2
*
L1-(AuCl)2 (4.4 mol %)
R1
R
Table 3. SKP L1/Au(I) Catalyzed Cyclopropanation of
trans-1,2-Disubstituted Alkenes 3
AgBF4 (4 mol %)
alkenes
O
+
9
PhF, 0 o
C
N
N
(dr > 20:1 in all cases)
10
11
12
13
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H
8
9
H
1
p-tBuC6H4
Ph
p-Tol
p-BrC6H4
H
O
H
H
O
H
O
O
9c
N
N
N
9a
2 h, 94%, 92% ee 0.1 h, 92%, 90% ee
n-Bu
9b
N
9d
H
H
H
H
5 h, 81%, 91% ee 0.3 h, 96%, 95% ee
Ph
Ph
2-naphthyl
*
*
Me
O
Me
O
H
O
H
O
F
time yield
(h) (%)a
ee
entry
1
3
6
(%)b
N
N
N
N
H
9e
9g
9h
H
H
9f
1c
2c
3
3a: Ar = Ph, R3 = Me
0.3
0.5
0.3
0.3
2.0
5.0
2.0
40
88
82
76
81
72
65
72
71
83
53
48
90
88
90
94
91
92
94
92
88
93
94
H
Me
1b
1c
1a
1d
1f
6a
6b
6c
6d
6e
6f
4 d, 18%, 70% ee
0.3 h, 98%, 94% ee
aIsolated yield. bFor details, see supporting information.
0.1 h, 83%, 93% ee
0.1 h, 66%, 86% ee
3a: Ar = Ph, R3 = Me
3b: Ar = PMP, R3 = Me
3b: Ar = PMP, R3 = Me
3b: Ar = PMP, R3 = Me
3b: Ar = PMP, R3 = Me
3b: Ar = PMP, R3 = Me
3b: Ar = PMP, R3 = Me
3b: Ar = PMP, R3 = Me
3c: Ar = PMP, R3 = CH2OMe
3c: Ar = PMP, R3 = CH2OMe
4
5c
6
1g
1h
1h
1i
7
6g
6g
6h
6i
8d
9
1.0
0.4
0.5
Figure 1. X-ray crystal structure of complex L1(AuCl)2.
10
11
1d
1f
In conclusion, we have developed a highly diastereo-
and enantioselective cyclopropanation of diazooxindoles
with various alkenes, including both cis and trans 1,2-
disubstituted alkenes, which contributes to the synthesis
of substituted spirocyclopropyloxindoles that are useful in
medicinal research. The high efficiency observed in this
reaction suggests the potential wide application of gold-
stabilized donor/acceptor carbenoids in the development
of asymmetric cyclopropanations. Our results also imply
that spiroketal bisphosphine ligands might find more
application in gold catalyzed asymmetric reactions, which
are still very limited.19 Further studies are in progress to
investigate the range of the new synthetic applications of
gold-stabilized donor/acceptor carbenoids.
6j
12
2.0
0.5
52
53
92
92
1e
6k
6l
3d: Ar =
R3 = Me
13c
1f 3d
b
c
aIsolated yield. Determined by chiral HPLC analysis. At -30
oC. Run on a 4.0 mmol scale, using 1.1 mol % of L1(AuCl)2,
d
ASSOCIATED CONTENT
and 1.0 mol % of AgBF4 at -30 oC.
Supporting Information. Experimental procedures,
characterization data, copies of NMR spectra, and HPLC
traces for all compounds. This material is available free of
charge via the Internet at http://pubs.acs.org.
The high stereoselectivity and broad substrate scope
achieved by SKP L1/Au(I) complex prompted us to get
more structure information, as SKP ligands contained a
unique spiroketal backbone, different from the widely
used axially chiral diphosphine ligands in gold catalysis.19
The X-ray diffraction analysis of the catalyst precursor
L1(AuCl)2 confirmed the formation of Au-Au interaction,
with a bond length of 3.25 Å, as shown in Figure 1. Be-
cause the best result was obtained with the ratio of
AgBF4/L1(AuCl)2 as 1:2, the active catalytic species might
be a monocationic complex, and the exact structure of
which is now in studies.
AUTHOR INFORMATION
Corresponding Author
jzhou@chem.ecnu.edu.cn
ACKNOWLEDGMENT
This article is dedicated to Prof. Guo-Qiang Lin on the
occasion of his 70th birthday.
We thank the financial support from NSFC (21172075,
21222204, 21232009), the 973 program (2011CB808600,
2010CB833300), Program for NCET in University (NCET-
11-0147), and Innovation Program of SMEC (12ZZ046).
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