Chapter 3: Hiyama Coupling Check Access

The use of silicon in organic synthesis is widespread due to its relatively high natural abundance, low cost and low toxicity. Its use in protecting groups will be familiar to many organic synthetic chemists because of its ease of application, removal and broad utility. This chapter aims to illustrate another rich area of silicon chemistry, that of the metal catalysed cross coupling reaction. The Hiyama and Hiyama–Denmark coupling reactions offer potential alternatives to the more widely used Suzuki–Miyaura coupling (SMC) reaction for the preparation of C(sp²)–C(sp²) bonds. The inherent low C–Si bond polarisation results in greater substrate stability and therefore improved chemoselectivity. This is elegantly demonstrated by a number of late stage Hiyama–Denmark coupling reactions for the preparation of complex natural products. In common with several other cross coupling methodologies, the introduction of more active catalytic systems has increased substrate scope and resulted in lower catalyst loadings.