Rhodium‐Catalyzed Hydrosilylation of Alkenes with Acylhydrosilanes

Abstract

Acylsilanes are an important class of organosilicon compounds that have gained increased attention recently. Their various reaction modes in particularly their ability to generate carbenes under thermal or photochemical conditions render them valuable reagents in organic synthesis. In this communication, an unprecedented route towards acylsilanes is reported by introducing the acylsilane moiety directly in a single step through alkene hydrosilylation. In this context, acylhydrosilanes representing a novel class of acylsilanes are introduced and applied as silylation reagents in rhodium catalyzed alkene hydrosilylations to access a great variety of acylsilanes. These reactions occur in good to excellent yields under mild conditions and show high functional group tolerance and atom economy.

Benzoyldiisopropylchlorosilane: a visible light photocleavable alcohol protecting group

“…Deprotonation of benzal bromide and subsequent reaction with commercial diisopropylchlorosilane provided the silane 5 that was further transformed to the benzoylsilane 6 by treatment with Ag 2 CO 3 in DCM, as recently reported by us (Scheme 2). 8 The chlorination of the hydrosilane 6 was readily achieved with trichloroisocyanuric acid (TCCA) in DCM at room temperature to afford the targeted benzoyldisopropylsilylchloride (BDIPSCl, 1a) in near quantitative yield. 9 The robustness of this sequence was demonstrated by the successful preparation of 1a on 50 mmol scale in a total yield of 83% over three steps, without the necessity of any column chromatography.…”

“…Deprotonation of benzal bromide and subsequent reaction with commercial diisopropylchlorosilane provided the silane 5 that was further transformed to the benzoylsilane 6 by treatment with Ag 2 CO 3 in DCM, as recently reported by us (Scheme 2). 8…”