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Article

Indium-Catalyzed Radical Reductions of Organic Halides with Hydrosilanes

Supporting Info

Katsukiyo Miura,*^† Mitsuru Tomita,^† Yusuke Yamada,^† and Akira Hosomi*^‡;

Department of Chemistry, 21st Century COE, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan, and Faculty of University Evaluation and Research, National Institution for Academic Degrees and University Evaluation, Kodaira, Tokyo 187-8587, Japan

J. Org. Chem., 2007, 72 (3), pp 787–792

DOI: 10.1021/jo061880o

Publication Date (Web): December 30, 2006

Corresponding authors. Phone: 81-298-534486; fax: 81-298-53-6503.

†

University of Tsukuba.

‡

National Institution for Academic Degrees and University Evaluation.

, miura@chem.tsukuba.ac.jp, ; , hosomi@chem.tsukuba.ac.jp

Abstract

The In(OAc)₃-catalyzed reaction of bromo- and iodoalkanes with PhSiH₃ in THF at 70 °C gave dehalogenated alkanes in good to high yields. In the presence of Et₃B and air, the reduction proceeded smoothly at 30 °C. When 2,6-lutidine and air were used as additives, the In(OAc)₃-catalyzed system enabled an efficient reduction of simple and functionalized iodoalkanes in EtOH. Catalytic use of GaCl₃ was found to be effective in the reduction of haloalkanes with poly(methylhydrosiloxane) (PMHS). These catalytic reductions probably involve a radical chain mechanism in which indium or gallium hydride species work as the actual reductants.

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History

Published In Issue February 02, 2007
Received September 12, 2006

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Article

Indium-Catalyzed Radical Reductions of Organic Halides with Hydrosilanes