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Synlett 2011(6): 813-816  
DOI: 10.1055/s-0030-1259914
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Siloles via Rhodium-Catalyzed Cyclization of Alkynes and Diynes with Hexamethyldisilane

Takanori Matsuda*, Yuya Suda, Yosuke Fujisaki
Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Fax: +81(3)52614631; e-Mail: matta@rs.kagu.tus.ac.jp;
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Publication History

Received 26 December 2010
Publication Date:
15 March 2011 (online)

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Abstract

A rhodium-catalyzed silylative cyclization of alkynes and 1,6-diynes with hexamethyldisilane is described. These reactions enable the synthesis of densely substituted silole derivatives through the use of a rhodium(I)-norborna-2,5-diene complex as a catalyst.

Key words

alkynes - cyclization - diynes - rhodium - siloles

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9

The attempted detection of tetramethylsilane formation was unsuccessful when the reaction was performed in C6D6 at 30 ˚C in a sealed NMR tube.

11

The reaction of a diyne with t-BuMe2SiH catalyzed by a rhodium(I) complex under an ambient pressure of carbon monoxide reportedly gave a silole via a mechanism involving a Si-Me bond cleavage. See ref. 5f.

12

When 1,6-enyne 8 was employed as the substrate, analogous silylative cyclization occurred to afford bicyclic dihydro-silole 9 in 44% isolated yield (Scheme  [4] ).

Scheme 4