Organic Letters
Letter
W.; Bickelhaupt, F. Synthesis 1985, 647. For related reactions of
unexpected aromatization via electrocyclic reactions of dihalocyclo-
propanes, see: (c) Banwell, M. G.; Ma, X.; Taylor, R. M.; Willis, A. C.
Org. Lett. 2006, 8, 4959. (d) Adekenov, S. Chem. Nat. Compd. 2013,
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smoothly. After protection of the secondary hydroxy group in 8
with a TBS group, the cyclopropanation and ensuing
electrocyclic reactions were conducted under the standard
conditions to give 11 in good yield.
In conclusion, we have demonstrated an efficient method for
constructing benzene rings from ester moieties. A variety of
functional groups survived the process, and the stereogenic
center at the α position to the carbonyl group was not affected
by the transformation. 4-Bromo- and 4-chlorophenyl groups
thus prepared are good substrates for a variety of coupling
reactions.11,12 Therefore, the method developed here will help
prepare a wide range of compounds for drug development.
Further applications of our method are currently underway and
will be reported in due course.
(6) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1,
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(7) Reactions of esters with organotitanium reagents giving
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(8) Evans, D. A.; Ennis, M. D.; Mathre, D. J. J. Am. Chem. Soc. 1982,
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(10) Lactone 6 was synthesized from commercially available
cyclohex-3-enecarboxylic acid in four steps, involving iodolactoniza-
tion, elimination of hydrogen iodide, stereoselective dihydroxylation,
and protection as an acetonide. For details, see the Supporting
Information.
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental details and spectroscopic data. The Supporting
AUTHOR INFORMATION
Corresponding Authors
■
(11) For selected reviews, see: (a) Miyaura, N.; Suzuki, A. Chem. Rev.
́
1995, 95, 2457. (b) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.;
Notes
Lemaire, M. Chem. Rev. 2002, 102, 1359. (c) Littke, A. F.; Fu, G. C.
Angew. Chem., Int. Ed. 2002, 41, 4176. (d) Corbet, J.-P.; Mignani, G.
Chem. Rev. 2006, 106, 2651.
(12) For selected reviews, see: (a) Hartwig, J. F. Acc. Chem. Res.
1998, 31, 852. (b) Ley, S. V.; Thomas, A. W. Angew. Chem., Int. Ed.
2003, 42, 5400. (c) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534.
(d) Ma, D.; Cai, Q. Acc. Chem. Res. 2008, 41, 1450. (e) Surry, D. S.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47, 6338. (f) Surry, D. S.;
Buchwald, S. L. Chem. Sci. 2010, 1, 13. (g) Furuya, T.; Kamlet, A. S.;
Ritter, T. Nature 2011, 473, 470. (h) Rao, H.; Fu, H. Synlett 2011,
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(j) Okano, K.; Tokuyama, H.; Fukuyama, T. Chem. Commun. 2014,
50, 13650.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by JSPS KAKENHI (Grant
Nos. 25221301 and 26713001) and Platform for Drug
Discovery, Informatics, and Structural Life Science (MEXT).
H.U. is a Research Fellow of JSPS.
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