Catalytic Asymmetric Synthesis of Chiral Spiro-cyclopropyl Oxindoles from 3-Alkenyl-oxindoles and Sulfoxonium Ylides

Article abstract of DOI:10.1002/adsc.201800937

A new enantioselective cyclopropanation of 3-alkenyl-oxindoles with sulfoxonium ylides was realized by using a chiral N,N′-dioxide/Mg(OTf)₂ complex as the catalyst. Various chiral spiro-cyclopropyl oxindoles containing two or three continuous chiral carbon centres were obtained in high yields (up to 99%) with good dr (up to 97:3 dr) and high ee values (up to 94% ee). (Figure presented.).

Full text of DOI:10.1002/adsc.201800937

Title: Catalytic Asymmetric Synthesis of Chiral Spiro-cyclopropyl
Oxindoles from 3-Alkenyl-oxindoles and Sulfoxonium Ylides
Authors: Lifeng Wang, Weidi Cao, Hongjiang Mei, Linfeng Hu, and
Xiaoming Feng
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800937
Link to VoR: http://dx.doi.org/10.1002/adsc.201800937

10.1002/adsc.201800937
Advanced Synthesis & Catalysis
Very Important Publication
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Catalytic Asymmetric Synthesis of Chiral Spiro-cyclopropyl
Oxindoles from 3-Alkenyl-oxindoles and Sulfoxonium Ylides
Lifeng Wang,a Weidi Cao,a,* Hongjiang Mei,a Linfeng Hu,a and Xiaoming Fenga,*
a
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University,
Chengdu 610064, People’s Republic of China
Fax: (+86)-28-8541-8249; e-mail: wdcao@scu.edu.cn; xmfeng@scu.edu.cn;
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
using La-Li3-(biphenyldiolate)3 catalysts.[14a] The
Abstract: A new enantioselective cyclopropanation of 3-
alkenyl-oxindoles with sulfoxonium ylides was realized by same group also reported the synthesis of chiral
using a chiral N,N-dioxide/Mg(OTf)2 complex as the
catalyst. Various chiral spiro-cyclopropyl oxindoles
containing two or three continuous chiral carbon centres
were obtained in high yields (up to 99%) with good dr (up
to 97:3 dr) and high ee values (up to 94% ee).
epoxides and oxetanes from ketones and
dimethyloxosulfonium methylide catalyzed by the
heterobimetallic catalysts.[14b-14d] Herein, we report
our efforts in developing an N,N-dioxide-Mg(II)
Table 1. Optimization of the reaction conditions.[a]
Keywords: asymmetric cyclopropanation; 3-alkenyl-
oxindoles; N,N-dioxides; sulfoxonium ylides; spiro-
cyclopropyl oxindoles
Spiro-cyclopropyl oxindoles motifs are widely
present in clinical pharmaceuticals and bioactive
compounds,[1] such as HIV inhibitors,[2] kinase
inhibitors[3] as well as antitumor agents.[4] Over the
past decades, several methodologies have been
developed for the construction of chiral spiro-
cyclopropyl oxindoles skeletons, mainly including
transition metal-catalyzed cyclopropanation of diazo
oxindoles with alkenes,[5] organocatalytic Michael-
initiated ring-closure reactions between ,-
unsaturated carbonyl compounds and 3-chloro-
oxindoles,[6] 3-alkylidene oxindoles and alkyl
halides,[7] oxindoles and bromo-nitroolefins.[8]
Alternatively, our group reported chiral Lewis acid-
Yield
[%][b]
ee
Entry Ligand
Metal salt
dr[c]
[%][c]
1
2
3
4
5
6
Ni(OTf)2
Zn(OTf)2
Mg(OTf)2
Mg(OTf)2
Mg(OTf)2
Mg(OTf)2
Mg(OTf)2
Mg(OTf)2
Mg(OTf)2
66
69
91
83
90
89
81
99
99
93:7
95:5
94:6
97:3
95:5
96:4
94:6
92:8
78:22
0
0
L-PiPr2
L-PiPr2
L-PiPr2
L-PrPr2
L-RaPr2
L-PiEt2
L-PiPr3
L-PiPr2
L-PiPr2
75
72
73
70
40
91
92
catalyzed
asymmetric
cyclopropanation
for
construction of spiro-cyclopropyl oxindoles.[9]
Phenyliodonium ylide was selected to generate in situ
free triplet carbene reacting with 3-alkenyl-oxindoles
in the presence of a chiral N,N-dioxide/Ni(II)
complex.[9a]
7
8[d]
9[e]
Sulfur (sulfonium and sulfoxonium) ylides[10] are
important synthetic intermediates for cyclization
reactions,[11] Stevens rearrangements,[10a,12] and they
can also be used as carbene precursors in various
carbene-participant reactions.[13] Among these
efficient transformations, the reports of catalytic
asymmetric reactions involving sulfoxonium ylide are
rare.[14] Shibasaki and Matsunaga described an
enantioselective cyclopropanation of enones and an
N-acylpyrrole with dimethyloxosulfonium methylide
[a]
Unless otherwise noted, the reactions were performed
with 1a (0.1 mmol), 2a (0.1 mmol), ligand/metal salt
(1:1, 10 mol%) and DMAP (1 equiv.) in CH2Cl2 (1.0
mL) under nitrogen atmosphere at 35 °C for 20 h.
Isolated yield.
Determined by chiral HPLC for the major
diastereoisomer.
DMAP (0.1 equiv.) was used. Reaction time was 16 h.
Without DMAP.
[b]
[c]
[d]
[e]
1
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10.1002/adsc.201800937
Advanced Synthesis & Catalysis
Table 2. Substrate scope of 3-phenacylideneoxindoles.[a]
ee),
along
with
slight
decreasing
of
diastereoselectivity (Table 1, entry 8). A lower
diastereoselectivity (78:22 dr) of the reaction was
observed without the use of DMAP (Table 1, entry 9).
On the basis of the ESI-MS analysis, a characteristic
signal of [DMAP+2a+Na+] at m/z 341.1286 (m/z
calcd 341.1294) was observed when mixing DMAP
with 2a, suggesting DMAP had an interaction with
sulfoxonium ylide, which may be the reason that
improving the diastereoselectivity of the reaction.
Therefore, the optimal reaction conditions were
established as L-PiPr2/Mg(OTf)2 (1:1, 10 mol%),
DMAP (0.1 equiv.) in CH2Cl2 at 35 C for 16 h.
The substrate scope was then evaluated. Diverse
C5 position-substituted oxindoles could react with 2a
smoothly to give the corresponding products 3aa-3ea,
3ga-3ia in 95-99% yield with 90:10-95:5 dr and 81-
93% ee (Table 2, entries 1-5 and 7-9). The absolute
configuration of 3ca was determined to be (2R,3R) by
X-ray crystallography analysis.[16] The reaction of 1f
bearing a strong electron-withdrawing group at the
C5 position was performed as well with 95:5 dr and a
moderate level of enantioselectivity (Table 2, entry 6).
Both C6 and C7 position-substituted 1j-1m were
tolerated, affording the products in 91-99% yields,
Yield
[%][b]
ee
Entry
R1
dr[c]
[%][d]
1
2
3
4
5
6
7
8
H
5-F
5-Cl
5-Br
5-I
5-O2N
5-F3CO
5-Me
5-MeO
6-F
6-Cl
6-Br
7-F
99 (3aa)
99 (3ba)
97 (3ca)
99 (3da)
95 (3ea)
81 (3fa)
98 (3ga)
99 (3ha)
99 (3ia)
93 (3ja)
97 (3ka)
99 (3la)
91 (3ma)
99 (3na)
92:8
93:7
95:5
95:5
95:5
95:5
90:10
92:8
92:8
92: 8
92:8
92:8
97:3
93:7
91
93
92
91
81
66
91
93
94
93
92
92
93
93
9
10
11
12
13
14
5,7-2Me
[a]
Unless otherwise noted, the reactions were performed
with L-PiPr2/Mg(OTf)2 (1:1, 10 mol%), 1 (0.1 mmol),
2a (0.11 mmol) and DMAP (0.1 equiv.) in CH2Cl2 (1.0
mL) under nitrogen atmosphere at 35 °C for 16 h.
Isolated yield.
Determined by chiral HPLC for the major
diastereoisomer.
Determined by chiral HPLC analysis.
Table 3. Substrate scope of 1 and sulfoxonium ylides.[a]
[b]
[c]
[d]
Yield
[%][b]
ee
complex catalytic system[15] for the catalytic
asymmetric cyclopropanation of 3-alkenyl-oxindoles
with sulfoxonium ylides to synthesize spiro-
cyclopropyl oxindole derivatives.
Entry R2, R3
dr[c]
[%][d]
1[e]
2
3
2-ClC6H4, 2-ClC6H4 61 (3ab) 87:13 93
3-ClC6H4, 3-ClC6H4 99 (3ac)
4-ClC6H4, 4-ClC6H4 98 (3ad) 95:5
95:5
91
88
89
90
Initially, N-Boc-3-phenacylideneoxindole 1a and
sulfoxonium ylide 2a were chosen as the model
substrates to optimize the reaction conditions.
Various metal salts were screened by coordinating
4
5
6
4-FC6H4, 4-FC6H4
4-BrC6H4, 4-BrC6H4
4-MeC6H4, 4-
MeC6H4
99 (3ae)
99 (3af)
75 (3ag)
94:6
94:6
87:13 94
with
L-PiPr2 in
the
presence
of
4-
7
4-MeOC6H4, 4-
MeOC6H4
4-FC6H4, Ph
4-ClC6H4, Ph
MeO, Ph
99 (3ah) 86:14 92
dimethylaminopyridine (DMAP) in CH2Cl2 at 35 C
(Table 1, entries 1-3). Both L-PiPr2/Ni(II) and L-
PiPr2/Zn(II) complexes could promote the reaction
but gave racemic products (Table 1, entries 1 and 2).
The desired product 3aa could be obtained in 91%
yield, 94:6 dr and 75% ee by using L-PiPr2/Mg(II)
complex as the catalyst (Table 1, entry 3). The
investigation of the chiral backbone of the N,N-
dioxide ligands showed that L-pipecolic acid derived
L-PiPr2 was superior to L-proline-derived L-PrPr2
and L-ramipril-derived L-RaPr2 in term of
enantioselectivity (Table 1, entry 3 vs. entries 4 and
5). Decreasing or increasing the steric hindrance of
the amide moiety of the N,N-dioxide ligands led to
lower enantioselectivities (Table 1, entry 3 vs. entries
6 and 7). Then the amount of DMAP was screened.
3aa could be obtained in 99% yield within 16 h in the
presence of 0.1 equiv. DMAP, the enantioselectivity
of the cyclopropanation was improved sharply (91%
8[f]
98 (3ai)
96 (3aj)
94 (3ak) 86:14 82
82 (3al) 95:5 77
85:15 83
86:14 83
9[f]
10[g]
11
Me, Me
[a]
Unless otherwise noted, the reactions were performed
with L-PiPr2/Mg(OTf)2 (1:1, 10 mol%), 1 (0.1 mmol),
2 (0.11 mmol) and DMAP (0.1 equiv.) in CH2Cl2 (1.0
mL) under nitrogen atmosphere at 35 °C for 16 h.
Isolated yield.
[b]
[c]
[d]
Determined by 1H NMR analysis.
Determined by chiral HPLC for the major
diastereoisomer.
The reaction was performed at 50 °C for 10 h.
L-PrPr2 was used instead of L-PiPr2.
L-PiEt2Me was used instead of L-PiPr2, DMAP (0.8
equiv.) was used.
[e]
[f]
[g]
2
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10.1002/adsc.201800937
Advanced Synthesis & Catalysis
92:8-97:3 dr and 92-93% ee (Table 2, entries 10-13).
The cyclopropanation of 5,7-dimethyl substituted 1n
with 2a successfully proceeded to give good results
(Table 2, entry 14).
Table 4. Control experiments.[a]
Scheme 1. Experimental results about other sulfur ylides.
[a]
The reactions were performed with L-PiPr2/Mg(OTf)2
(1:1, 10 mol%), 1 (0.1 mmol), 2a (0.11 mmol) and DMAP
(0.1 equiv.) in CH2Cl2 (1.0 mL) under nitrogen atmosphere
at 35 °C for 16 h. Isolated yield. Dr was determined by 1H
NMR analysis. Ee was determined by chiral HPLC for the
major diastereoisomer.
Subsequently, we turned our attention to exploring
the effects of the substituents R2 and R3 of acyl motifs
in substrates 1 and 2. The ortho-chloro-substituted
product 3ab was obtained in a lower yield than those
with meta- or para-chloro-substituents (Table 3, entry
1 vs. entries 2 and 3). The enantioselective
cyclopropanation could proceed smoothly no matter
what R2 and R3 were electron-donating or electron-
withdrawing substituents at para-position of the
phenyl group, providing 3ad-3ah in 75-99% yields,
86:14-95:5 dr and 88-94% ee (Table 3, entries 4-7). It
was worth to note that the product 3ai3ak which
contained three continuous chiral carbon centers were
obtained with good results (Table 3, entries 8-10). 3al
(R2 = R3 = Me) could also be achieved in 82% yield,
95:5 dr with 77% ee (Table 3, entry 11). In addition,
some other sulfonium ylides were also explored
under the standard conditions. Stabilized sulfonium
ylide reacted with 1a smoothly and gave the desired
product 3aa in 95% yield with 72:28 dr and 69% ee
(Scheme 1a). The non-stabilized ylide like
dimethyloxosulfonium methylide reacted with 1a,
affording the product 4 in 35% yield, 57:43 dr and
16%/5% ee (Scheme 1b).
To evaluate the synthetic potential of this
methodology, a gram scale reaction of 3ca was
carried out. 1c (2.5 mmol) reacted with sulfoxonium
ylide 2a (2.75 mmol) smoothly, affording the desired
product 3ca in 98% yield (1.22 g), 95:5 dr and 92%
ee (Scheme 2a). Furthermore, treating the product
3ca with triethyl silane and boron trifluoride accessed
5 in 93% yield without loss of stereoselectivity
(Scheme 2b).
Next, several control experiments were performed
to investigate the mechanism of the cyclopropanation
between 3-alkenyl-oxindoles and sulfoxonium ylides
(Table 4). When 3-phenacylideneoxindole or N-Bn-3-
phenacylideneoxindole was used instead of bidentate
1a to react with 2a, products 6a or 6b were obtained
without any enantioselectivity. The yields of products
6a and 6b are low no matter with or without L-
PiPr2/Mg(OTf)2 complex in the reaction, suggesting
that N-H and N-Bn substrates has low activities
1
owing to lower electrophilicity. In addition, H NMR
spectra suggested that the acidic proton N-H of
substrate interferes with the sulfoxonium ylide.[17]
When an acetyl group was induced as a protecting
group, the reaction could proceed well and afforded
the desired product 6c in 81% yield with 11% ee
under condition B. When the reaction without L-
PiPr2/Mg(OTf)2, the yield of 3aa product reduced to
67%. These results suggested that the Boc group
Scheme 2. Scale-up reaction and derivatization.
3
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10.1002/adsc.201800937
Advanced Synthesis & Catalysis
mg, 10 mol%) and the ligand L-PiPr2 (6.5 mg, 10 mol%)
in anhydrous CH2Cl2 (1.0 mL) under nitrogen atmosphere.
The mixture was stirred at 35 °C for 0.5 h followed by
addition of sulfoxonium ylide 2a (0.11 mmol) and DMAP
(1.2 mg, 0.1 equiv.) and then continued to stir at 35 °C for
another 16 h. The residue was purified by flash
chromatography on silica gel (ethylacetate/petroleum ether
= 1:9 – 1:4) to afford the desired products.
combining to the nitrogen atom played a crucial role
in achieving high reactivity and stereoselectivity.
Based on the X-ray crystal structure of the L-
PiPr2/Mg(OTf)2 complex,[18] as well as the control
experiments and our previous works,[15c] N-Boc-3-
phenacylideneoxindole as the electron-deficient 2π
component, the L-PiPr2/Mg(OTf)2 complex can
lower the LUMO energy to increase its
Acknowledgments
electrophilicity.
On the other hand, the
nucleophilicity of the sulfoxonium ylide will decrease
if its carbonyl groups combine with the L-
PiPr2/Mg(OTf)2 complex, which is against the first
nucleophilic attack step. Thus, we tend to think that
We appreciate the National Natural Science Foundation of China
(No. 21572136 and 21432006) for financial support.
the
alkenyloxindole was superior to sulfoxonium ylide in
this cyclopropanation. Meanwhile, possible
catalyst
coordinates
with
N-Boc-3-
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10.1002/adsc.201800937
Advanced Synthesis & Catalysis
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[18] CCDC 1838115 [L-PiPr2/Mg(OTf)2 complex]
5
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10.1002/adsc.201800937
Advanced Synthesis & Catalysis
COMMUNICATION
Catalytic Asymmetric Synthesis of Chiral Spiro-
cyclopropyl Oxindoles from 3-Alkenyl-oxindoles
and Sulfoxonium Ylides
Adv. Synth. Catal. Year, Volume, Page – Page
Lifeng Wang,a Weidi Cao,a,* Hongjiang Mei,a
Linfeng Hu,a and Xiaoming Fenga,*
6
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