Because carbon–heteroatom (C–X) bonds are prevalent in organic compounds, the development of reliable and efficient methods for construction of such bonds is of highly practical value. Transition metal–catalyzed insertion of carbenes into heteroatom–hydrogen bonds (X–H, X = O, N, S, etc.) provides one of the most efficient approaches to the formation of C–X bonds. Remarkable advances have been made in the development of methodology for catalytic asymmetric diazo insertion into C–H bonds, but only limited success has been achieved for asymmetric diazo insertions into heteroatom–hydrogen bonds. By using chiral spiro bisoxazoline ligands SpiroBOXs and diimine ligands SIDIMs, a series of catalytic asymmetric insertion of α-diazoesters into N–H, O–H, S–H, and Si–H bonds was developed with high to excellent enantioselectivities.
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