Acylsilanes in Rhodium(III)‐Catalyzed Directed Aromatic C–H Alkenylations and Siloxycarbene Reactions with CC Double Bonds1. (19th November 2013)

• Record Type: Journal Article
• Authors: Becker, Peter; Priebbenow, Daniel L.; Pirwerdjan, Ramona; Bolm, Carsten
• Is Part Of: Angewandte Chemie. Volume 126:Number 1(2014)
• Page Start: 273
• Page End: 275
• Publication Date: 2013-11-19
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201307446
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 <italic>ortho‐</italic>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 <italic>ortho</italic>‐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.</p> </abstract>