A general method for E-selective olefination of acylsilanes with isocyanides via silver catalysis

Abstract

Trisubstituted alkenes are valuable intermediates in synthetic organic chemistry. The olefination of acylsilanes is expected to be a useful method for preparing trisubstituted alkenes with a silyl substituent. However, only a few studies exist on this process. Here, a silver-catalyzed olefination reaction between acylsilanes and isocyanides is developed, resulting in E-vinylsilanes with good yields and moderate to excellent stereoselectivities. This method is characterized by its simplicity and generality, applicable to various types of both acylsilanes and isocyanides. Experimental investigations and density functional theory calculations support the notion that the size of the silyl group and the formation of a rigid annular intermediate are critical factors influencing the stereocontrol outcome.