Abstract

It is shown that a cationic rhodium(I)/biphep complex catalyzes the cycloisomerization of 2-(alkynylsilylethynyl)phenols, leading to alkynylmethylidene-benzoxasiloles through concomitant silicon and carbon migration. This unprecedented cycloisomerization presumably proceeds via the formation of rhodium vinylidenes through 1,2-silicon migration, followed by 1,3-carbon (alkyne) migration via the formation of hypervalent silicon centers.

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