Photoinduced C-O bond cleavage for copper-catalyzed allenyl radical cyanation

摘要

The selective activation and transformation of C-O bonds under mild conditions is of great significance in synthetic chemistry because of the widespread existence of carbon-oxygen single bonds. In this work, allenyl radicals were generated by the photoinduced cleavage of carbon-oxygen bonds, and participated in the copper catalytic cycle, affording structurally diverse and highly significant allenyl nitriles. Both 1,3-disubstituted allenyl nitriles and trisubstituted allenyl nitriles could be assembled with moderate to good yields (24 examples, 65-95% yields) and high chemoselectivity. To prove the utility of this new methodology, an allene nitrile was converted into other valuable synthetic blocks including an allyl nitrile, alkyl nitrile and alpha-cyano cyclic ketone.

关键词