Acylsilanes in Rhodium(III)‐Catalyzed Directed Aromatic C–H Alkenylations and Siloxycarbene Reactions with CC Double Bonds |
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| Authors: | Peter Becker Dr. Daniel L. Priebbenow Ramona Pirwerdjan Prof. Dr. Carsten Bolm |
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| Affiliation: | Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany) |
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| 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? C double or triple bonds remains virtually unexplored. To facilitate such a study, previously inaccessible aromatic acylsilanes containing an ortho‐tethered C? 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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| Keywords: | acylsilanes carbenes C– H functionalization photochemistry rhodium catalysis |
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