Stereoselective C-C bond-forming reactions through C(sp³)-H bond insertion of metal carbenoids

This chapter discusses metal carbenoids derived from a-diazocarbonyl compounds. It explores how the complex relationship between the catalyst and the substrate affects the chemo-, regio-, diastereo-, and enantioselectivity of C-C bond formation through C(sp³)-H bond insertion by metal carbenoids. A challenging aspect in organic chemistry for decades has been the stereoselective carbon-carbon bond formation by activation of a C(sp³)-H bond in the synthesis of pharmaceuticals, natural products, and other industrially relevant targets. Efficient and selective C-H insertion requires a carbenoid intermediate of appropriate reactivity and electrophilicity. An intermolecular C-H insertion reaction consists of three components: a diazo compound, a substrate that may contain a range of functional groups, and a transition metal catalyst. When carrying out an intramolecular C(sp³)-H insertion, factors affecting chemoselectivity can be broken down into three sections: diazo compounds, catalyst effects, and substrate functional groups.