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

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.

alkynes - cyclization - diynes - rhodium - siloles

References and Notes

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<A NAME="RU11410ST-9">9</A>

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

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<A NAME="RU11410ST-11">11</A>

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.

<A NAME="RU11410ST-12">12</A>

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