Copper-catalyzed 1,4-protosilylation and 1,4-protoborylation of enynic orthoesters for synthesis of functionalized 2,3-allenoates

Herein, copper-catalyzed 1,4-protosilylation and 1,4-protoborylation of enynic orthoesters have been de-veloped. The enynic orthoesters as precursors of unstable enynic esters were applied to produce the func-tionalized 2,3-allenoate products. Meanwhile, the asymmetric 1,4-protosilylation of enynic orthoesters with PhMe2Si-Bpin was also studied. The chiral monopyridine imidazoline ligand was efficient to pro-vide the asymmetric 1,4-protosilylation products with high enantioselectivity.& COPY; 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

Copper-catalyzed 1,4-protosilylation and 1,4-protoborylation reactions of enynic orthoesters were developed. The enynic orthoesters, as precursors of unstable enynic esters, were used to produce functionalized 2,3-allenoate products. The asymmetric 1,4-protosilylation of enynic orthoesters with PhMe2Si-Bpin was also studied, and the chiral monopyridine imidazoline ligand exhibited high enantioselectivity.