ChemComm
DOI: 10.1039/C4CC07P24a6gDe 4 of 4
COMMUNICATION
Journal Name
Wang, J. Xiao, Asian J. Org. Chem. 2014, 3, 1036.
excellent stereoselectivity but with a poor yield (eq. 7). This
result suggested that the (Z/E)-isomers had no obvious
influence on the stereoselectivity, but they exhibited different
reactivity. In contrast to the orientation of (E)-3-methyl-2-
vinylindole 2e in TS-I (Scheme 6), the indole moiety or the Ar
group in the structure of (Z)-2i was overlapped with one of the
two aromatic rings in that of the vinyliminium intermediate
(Scheme 7, TS-III or TS-IV). This overlapped orientation led to
a steric repulsion between the two reaction components, thus
3
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4
5
greatly reducing the reactivity of (Z)-2i
.
Moreover, halogen-substituted products
3
could easily
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undergo some cross-coupling reactions. For instance, product
3ea smoothly participated in a Suzuki coupling with 4-
J. Kimura, S. Takano, Jpn. Kokai Tokkyo Koho 2004
, JP
chlorophenylboronic acid to generate compound
7 in an
2004051503 A 20040219.
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excellent yield of 92% and retained enantioselectivity (eq. 8).
6
7
8
Cl
Bn
Bn
Br
N
1.5eq 4-ClPhB(OH)2
2 eq Cs2CO3
N
O
Ph
O
(8)
Ph
Me
Me
2014, 47, 1296; e) J. Adrio, J. C. Carretero, Chem. Commun. 2014
50, 12434.
,
0.06eq Butyldi-1-adamantylphosphine
0.05eq Pd(OAc)2
N
N
HN
96% ee
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H
DME, 80 oC, 15 h
HN
H
7
3ea
92%, 95% ee
Conclusions
Products, John Wiley & Sons, INC, New York, 2002
.
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In summary, we have established an organocatalytic
asymmetric formal [3+2] cycloaddition of isatin-derived 3-
indolylmethanols with 3-methyl-2-vinylindoles, leading to
highly
stereoselective
construction
scaffold
of
with
spiro[cyclopenta[b]indole-1,3'-oxindole]
concomitant creation of three contiguous stereogenic centers
(72-99% yield, all >95:5 dr, 90-98% ee), one of which is an all-
carbon quaternary stereogenic center. This transformation has
provided good examples for 3-indolylmethanol involved
enantioselective cycloadditions. Furthermore, this synthetic
strategy will not only open a new window for developing new
class of 3C building blocks in catalytic asymmetric
cycloadditions, but also provide a powerful tool in synthesizing
optically pure spirooxindoles with potential bioactivities.
9
,
Notes and references
a
School of Chemistry and Chemical Engineering, Jiangsu Normal
University, Xuzhou, 221116, China; Tel: +86(516) 83500065; E-mail:
†
Electronic Supplementary Information (ESI) available: Experimental
10 For an enantioselective multi-step cyclization: a) B. Xu, Z.-L. Guo,
details, optimization of conditions, characterization, original NMR and
HPLC spectra of all products, single crystal data of product 3ae. See
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13 CCDC 1017240, see ESI for details.
4 | J. Name., 2012, 00, 1-3
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