Catalytic asymmetric cyclopropanation with diazooxindole

Article abstract of DOI:10.1055/s-0032-1317746

The first catalytic asymmetric cyclopropanation using styrene and diazooxindole was achieved with Rh₂(S-PTTL)₄. The reaction proceeded smoothly with 1 mol% catalyst loading to provide a good yield of the biologically important spiro-cyclopropyloxindole product with moderate to good enantioselectivity and excellent diastereoselectivity. Georg Thieme Verlag Stuttgart · New York.

Full text of DOI:10.1055/s-0032-1317746

LETTER
▌29
letter
Catalytic Asymmetric Cyclopropanation with Diazooxindole
Chiral Spiro Cyclopropyloxindole
Atsuko Awata, Takayoshi Arai*
Department of Chemistry, Graduate School of Science, Chiba University, Inage, Chiba 263-8522, Japan
Fax +81(43)2902889; E-mail: tarai@faculty.chiba-u.jp
Received: 12.10.2012; Accepted after revision: 12.11.2012
The catalytic asymmetric cyclopropanation using various
olefins with diazooxindoles would provide a reliable
method for preparing chiral spiro cyclopropyloxindoles
Abstract: The first catalytic asymmetric cyclopropanation using
styrene and diazooxindole was achieved with Rh (S-PTTL) . The
reaction proceeded smoothly with 1 mol% catalyst loading to pro-
2
4
vide a good yield of the biologically important spiro-cyclopropyl- containing various functional groups (Scheme 1). Carreira
oxindole product with moderate to good enantioselectivity and et al. (2003) reported a racemic synthesis of spiro cyclo-
excellent diastereoselectivity.
propyloxindoles through cyclopropanation with diazoox-
1
3
Key words: asymmetric catalysis, spiro compounds, carbenoids, indole for the total synthesis of spirotryprostatin B. This
cyclopropanation, oxindole
report describes a catalytic asymmetric synthesis of spiro
cyclopropyloxindoles through transition-metal-catalyzed
asymmetric cyclopropanation with diazooxidole.
Spirooxindole is a privileged heterocyclic motif that ex-
ists in a large number of bioactive natural alkaloids and
Cl
Cl
pharmaceutical candidates.1–3 For example, MI-219 is an
Me
NH
O
HO
OH
inhibitor of the p53-MDM2 protein–protein interaction
H
4
NH
(
Figure 1). A highly functionalized spiro cyclobutyloxin-
NC
Me
Me
dole, welwitindolinone A isonitrile isolated from blue-
green algae by Moore et al. possesses antifungal activi-
F
MeO
O
O
5
,6
N
N
ty. Recently, spirooxindoles having spiro[2,4]system
have been studied for application to medicinal chemistry.
Spiro cyclopropyloxindole 1, especially, is a potent HIV-1
Cl
H
H
Ml-219
(–)-welwitindolinone A
isonitrile
7
non-nucleoside reverse transcriptase inhibitor. Spiro ep-
oxyoxindole 2 also shows biological activity as a potent
S
O
O
inhibitor of differentiation in promyelocytic leukemia
R1
Cl
Ph
8
cells. The biological activity of many organic compounds
O
O
is closely linked to stereochemistry, a phenomenon re-
ferred to as the ‘lock-and-key’ model. Because of the po-
tent biological importance of these compounds, catalytic
enantio- and diastereoselective methods are needed for
the synthesis of the spirooxindole framework.
N
N
H
H
1
R = H or Me
1
2
HIV-nonnucleoside reverse
transciptase inhibitor
antitubercular agents
Figure 1 Biologically active spirooxindole compounds
The enantioselective synthesis of these scaffolds is diffi-
cult because they have a highly hindered spirocyclic qua-
ternary carbon center. Specifically, the catalytic chiral
asymmetric synthesis of spirooxindole containing a cy-
N2
ML*
R2
R3
ML*
+
clopropane ring remains a challenging task in the current
O
O
organic synthesis.9,10 In a program for the development of
N
R1
N
H
H
biologically significant compounds, the stereoselective
construction of spirooxindoles has also been of our inter-
3
4
5
1
1
R1
R3
est. Recently, Baltoli and Bencivenni et al. reported the
first enantioselective access to spiro cyclopropyloxin-
doles via an organocatalytic Michael–alkylation cascade
reaction using methyleneindolinone and bromonitrometh-
ane to give the nitrofunctionalized spiro cyclopropyloxin-
doles.12 For accessing the spiro cyclopropyloxindoles,
metal-catalyzed cyclopropanation using diazo com-
pounds of alkenes has provided an alternative approach.
∗
∗
R2
∗
O
N
H
6
Scheme 1 Catalytic asymmetric synthesis of spiro cyclopropylox-
indole via a metal carbenoid intermediate
Racemic cyclopropanation of the diazooxindole and sty-
rene with several metal salts was examined initially (Ta-
ble 1). A solution of diazooxindole in dichloromethane
SYNLETT 2013, 24, 0029–0032
Advanced online publication: 11.12.2012
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
DOI: 10.1055/s-0032-1317746; Art ID: ST-2012-U0880-L
Georg Thieme Verlag Stuttgart · New York
©

30
A. Awata, T. Arai
LETTER
was added slowly to a mixture of styrene, metal salt, and
solvent at room temperature. Initially, Cu(I) triflate, an ef- oxindole
Table 2 Catalytic Asymmetric Cyclopropanation with Diazo-
1
4
ficient catalyst for cyclopropanation, was used. Howev-
er, the reaction became sluggish, despite consumption of
the diazooxindole (Table 1 entry 1). The use of the more
electron-enriched ethyl vinyl ether also failed to give the
desired product. The reaction using [Ru(p-cymene)Cl2]2
resulted in only a trace amount of product (Table 1 entry
Ph
N2
catalyst (x mol%)
CH2Cl2, 30 min
O
O
+
Ph
N
N
H
H
slow addition (3 h)
1
5
2). In addition, Cu(I) and Co(II) acetate did not promote
O
O
the reaction, and starting material was recovered (Table 1,
N
S
N
1
6
entries 3 and 4). In contrast, Rh (OAc) smoothly cata-
2
4
H
O
H
O
lyzed the reaction to give the cylopropanation adduct in
O
O
O
O
9
7% yield with 95:5 diastereoselectivity (Table 1, entry
1
7
Rh
Rh
Rh
Rh
5). The NOE analysis of the major product revealed that
the amide moiety of oxindole and the phenyl group was in
Rh2(S-TBSP)4
Rh2(S-PTTL)4
trans configuration (see Supporting Information).
Entry Catalyst
X
Temp Yield trans/cis ee of trans
°C) (%)a (%)
b
(%)
(
Table 1 Racemic Cyclopropanation of Diazooxindole
Ph
1
2
3
4
5
Rh (S-TBSP)
5
r.t.
r.t.
0
77
90
94:6
97:3
98:2
97:3
98:2
97:3
8
61
66
66
66
66
2
4
4
4
4
4
4
N2
Rh (S-PTTL)
5
catalyst (10 mol%)
2
+
Ph
O
O
CH2Cl2, r.t.
0 min
N
Rh
2
(S-PTTL)
2.5
2.5
1
>99
31
N
3
H
H
trans
Rh (S-PTTL)
–40
0
2
slow addition (3 h)
Rh (S-PTTL)
>99
>99
2
Entry
Metal salt
Yield (%)
trans/cis
6c
Rh (S-PTTL)
1
0
2
1
CuOTf
n.o.b
trace
n.r.b
n.r.b
>99
–
–
–
a
Combined yield of diastereomer.
Determined by crude NMR.
Diazooxindole was added in one portion and stirred for 1 h.
2a
3
[Ru(p-cymene)Cl2]2
CuOAc
b
c
4
Co(OAc)2
Rh (OAc)
at the 4-position on the phenyl ring gave the product in
moderate enantioselectivity with excellent diastereoselec-
tivity (Table 3, entries 1 and 4). 4-Methylstyrene afforded
the product with similar selectivity (Table 3, entry 5). The
reaction using 4-methoxystyrene was also possible and
produced a high chemical yield of product with 48% ee
5a
95:5
2
4
a
Conditions: 5 mol% catalyst were used.
n.o. = not obtained; n.r. = no reaction.
b
Initial screening of metal salts resulted in the use of chiral (Table 3, entry 6). The reaction using 1-pentene gave the
rhodium(II) catalyst, and results summarizing commer- product in 65% yield with acceptable diastereoselectivity
cially available chiral rhodium catalysts are shown in Ta- (trans/cis = 88:12, Table 3, entry 7). The trans product ex-
ble 2. Davies et al. showed that the proline-derived chiral hibited greater enantioselectivity in up to 74% ee.
dirhodium carboxylate, Rh (S-TBSP) , is an effective cat-
2
4
The high trans selectivity observed in Tables 1–3 is ex-
alyst for enantioselective cyclopropenation reactions with
plained in Scheme 2. For the Rh-catalyzed cyclopropana-
aryl diazoacetates.18 Although Rh (S-TBSP) smoothly
18c,20
2
4
tion using aryl diazoacetate,
the styrene attacks with
promoted the reaction, product was obtained in only 8%
ee (Table 2, entry 1). However, Rh (S-PTTL) , which was
developed by Hashimoto et al., provided enantiomerically
enriched spiro cyclopropyloxindole (Table 2, entry 2).
its phenyl group pointing away from the bulky rhodium
surface to avoid unfavorable interaction (TS1 in Scheme
2
4
2
). The C=C bond of styrene is expected to approach from
1
9
the amide side because a partial positive charge in the α-
The reaction proceeded in a highly trans-selective manner
to give the product in 90% yield with 61% ee. Although
the reaction at –40 °C did not improve the enantioselectiv-
ity, the catalyst loading could be reduced to 1 mol% (Ta-
ble 2, entry 5). Furthermore, similar yield and selectivity
were obtained by addition of a dichloromethane solution
of diazooxindole in one portion (Table 2, entry 6).
position of the phenyl group is stabilized by the negative
22,23
charge of the amide oxygen (TS2).
Then, the alkene
rotates to form spiro cyclopropyloxindole (TS3). As a re-
sult, the trans relation of the amide carbonyl and phenyl
group is expected to be the most favorable. The reaction
mechanism via the perpendicular approach of the alkene
19f,21
to the rhodium(II)–carbon axis is also possible.
The substrate scope of the Rh(II)-catalyzed cyclopropana-
tion was explored, and the results are summarized in Ta-
ble 3. Styrenes containing an electron-withdrawing group
In conclusion, the chiral rhodium-catalyzed catalytic
asymmetric cyclopropanation of diazooxindole for con-
Synlett 2013, 24, 29–32
© Georg Thieme Verlag Stuttgart · New York

LETTER
Chiral Spiro Cyclopropyloxindole
31
mL) were added at 0 °C. After stirring for 1 h, the solvent was re-
moved under reduced pressure, and the diastereomeric ratio was de-
termined by crude H NMR analysis. The resulting crude mixture
Table 3 Catalytic Asymmetric Cyclopropanation of Diazooxindole
with Various Olefins
a
1
R
was purified by silica gel column chromatography (hexane–EtOAc
N2
1
=
2:1 to 0:1) to afford the cyclopropyloxindole. H NMR (500 MHz,
Rh(S-PTTL)2 (1 mol%)
CDCl ): δ = 9.39 (br, 1 H), 7.30–7.19 (m, 5 H), 7.08 (t, J = 7.7 Hz,
3
O
+
O
R
1 H), 6.96 (d, J = 7.5 Hz, 1 H), 6.66 (m, 1 H), 5.95 (d, J = 7.5 Hz, 1
H), 3.36 (t, J = 8.6 Hz, 1 H), 2.24–2.21 (m,1 H), 2.04–2.02 (m, 1 H);
CH2Cl2 (0.06 M)
0 °C, 1 h
N
N
H
H
13
C NMR (125 MHz, CDCl ): δ = 179.1, 141.1, 134.9, 130.0, 128.3,
3
Entry
R
Yield (%)b trans/cis (%)c ee of trans (%)
127.9, 127.4, 126.5, 121.4, 120.9, 109.7, 36.1, 33.7, 22.6; HRMS:
m/z calcd for C H NO [M – H]: 234.0924; found: 234.0928; IR
1
6
12
–
1
25.3
D
(
1
neat): 2922, 1704, 1619, 1467, 1218 cm ; [α] = +104.3 (c =
.0, CHCl , 98:2 dr, 66% ee); Enantiomeric excess was determined
1
2
3
4
5
6
4-ClC H4
>99
98
97:3
98:2
96:4
96:4
96:4
93:7
88:12
65
60
66
64
62
48
74
6
3
3-ClC H4
by HPLC with a Chiralpack AD-H column [hexane–2-PrOH
6
(
70:30), 1.0 mL/min, 254 nm]; t (minor enantiomer) = 5.1 min; t
R
R
2-ClC H4
92
6
(major enantiomer) = 6.3 min.
4-FC H4
>99
>99
>99
65
6
Acknowledgment
4-MeC H4
6
This work was supported by a Grant-in-Aid for Scientific Research
from the Ministry of Education, Culture, Sports, Science and Tech-
nology, Japan, and the Takeda Science Foundation.
4-MeOC H4
6
7
n-C H5
3
a
Diazooxindole was added in one portion and stirred for 1 h.
Combined yield of diastereomers.
Determined by crude NMR.
b
c
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett. SnuIpofoipmngr irtSatnoIuipfog
r
t
iornat
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General Procedure for the Catalytic Asymmetric Cyclopropa-
nation with Styrene and Diazooxindole (Table 2, Entry 6)
Rh (S-PTTL) (0.0015 mmol, 2.1 mg) was added to a two-necked
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Styrene (0.75 mmol) and diazooxindole (0.15 mmol) in CH Cl (2.0
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©
Georg Thieme Verlag Stuttgart · New York
Synlett 2013, 24, 29–32

3
2
A. Awata, T. Arai
LETTER
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Synlett 2013, 24, 29–32
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