T. Zhang et al. / Tetrahedron Letters 50 (2009) 1290–1294
1293
O
O
Acknowledgments
Me
H
We are grateful to the National Natural Science Foundation of
China (Project No. 20732005) and National Basic Research Program
of China (973 Program, 2009CB825300) and CAS Academician
Foundation of Zhejiang Province for financial support.
+
8
8
SO2
Me
5f'
SO2
H
Ph
5f
H
Ph
Supplementary data
11: 1
Figure 2. NOE experiment on the mixture of 5f and 5f0.
Supplementary data associated with this article can be found, in
References and notes
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O
O2
S
TMS
OTf
R1
Ar
R2
R3
or
2
1
4
Arylation Products
H
F
-HF
O
F
K
O
O2
S
R2
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R1
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O
O
O
K
R2
R3
R2
R3
R2
H
R1
R1
R1
R3
Ar
O2S
K
O2S
SO2
Ar
5
Ar
9
or
3
10
Scheme 1. The plausible mechanisms for insertion of arynes into C–C and ring
expansion processes.
4. Himeshima, Y.; Sonoda, T.; Kobayashi, H. Chem. Lett. 1983, 1211.
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O
O
Raney Ni (excess)
EtOH, reflux
R1
R1
n
n
6. (a) Tambar, U. K.; Stoltz, B. M. J. Am. Chem. Soc. 2005, 127, 5340; (b) Yoshida,
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O2S
Ar
5
11
O
O
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V. Org. Biomol. Chem. 2005, 3, 3297; (b) Clayden, J.; Kenworthy, M. N.;
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10
7
11a:
99%, 2h
11b:
95%, 5h
Scheme 2. Hydrogenolysis of aryl sulfonyl-substituted ring expansion products.
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amalgam route) (a) Shimamura, H.; Sunazuka, T.; Izuhara, T.; Hirose, T.; Shiomi,
K.; Omura, S. Org. Lett. 2007, 9, 65; (b) Yamamoto, K.; Shimizu, M.; Yamada, S.;
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mation of seven- to ten-membered benzo rings. After being re-
quired in the ring expansion procedure, the redundant aryl sulfo-
nyl groups were exchanged to hydrogen atoms via the
hydrogenolysis effect induced by Raney Ni, and benzo cyclic ke-
tones were obtained in high yields. The details of mechanism
and further applications of products are being investigated.