Mechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X–H and C(sp2)–H bonds

This review provides a mechanistic overview of asymmetric Fe, Cu, Pd, Rh, Au and heme-based enzymes catalyzed carbene insertion reactions to construct C–X (X = O, N, S, etc. ) and C–C bonds, focusing on the stereochemical models.