Metal-catalysed C-C bond formation at cyclopropanes.

Cyclopropanes are important substructures in natural products and pharmaceuticals. Although traditional methods for their incorporation rely on cyclopropanation of an existing scaffold, the advent of transition-metal catalysis has enabled installation of functionalized cyclopropanes using cross-coupling reactions. The unique bonding and structural properties of cyclopropane render it more easily functionalized in transition-metal-catalysed cross-couplings than other C(sp) substrates. The cyclopropane coupling partner can participate in polar cross-coupling reactions either as a nucleophile (organometallic reagents) or as an electrophile (cyclopropyl halides). More recently, single-electron transformations featuring cyclopropyl radicals have emerged. This Review will provide an overview of transition-metal-catalysed C-C bond formation reactions at cyclopropane, covering both traditional and current strategies, and the benefits and limitations of each.