Acylsilanes in Rhodium(III)-Catalyzed Directed Aromatic C–H Alkenylations and Siloxycarbene Reactions with C[BOND]C Double Bonds

Authors


  • D.L.P. acknowledges support by the Alexander von Humboldt foundation.

Abstract

Acylsilanes are known to undergo a 1,2-silicon-to-oxygen migration under thermal or photochemical conditions to form siloxycarbenes. However, there are few reports regarding the application of siloxycarbenes in organic synthesis and surprisingly, their reaction with C[BOND]C double or triple bonds remains virtually unexplored. To facilitate such a study, previously inaccessible aromatic acylsilanes containing an ortho-tethered C[BOND]C double bond were identified as suitable substrates. To access these key intermediates, we developed a new synthetic method utilizing a rhodium-catalyzed oxidative Heck-type olefination involving the application of an acylsilane moiety as a directing group. When exposed to visible-light irradiation, the ortho-olefinated acylsilanes underwent a smooth intramolecular cyclization process to afford valuable indanone derivatives in quantitative yields. This result paves the way for the development of new transformations involving siloxycarbene intermediates.

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