The Cu/Pd-catalyzed boryldifluoroallylation of alkynes was achieved, providing the skipped gem-difluorodiene scaffolds with high regio- and stereoselectivity. An array of synthetic building blocks can be obtained via further transformations.

A unique and practical Cu-catalyzed cisalkynylboration of terminal alkynes with diboron reagents and bromoalkynes has been realized. This process enables the convenient synthesis of a large variety of trisubstituted enynylboronates under mild reaction conditions with broad functional-groups compatibility, high regioselectivity and stereoselectivity. The usability and practicability of this process was further demonstrated by the successful modular synthesis of enediynes. Scheme 3. Gram-scale experiment and derivatization of product. Scheme 4. Modular synthesis of enediynes from three simple alkynes. Scheme 5. Plausible catalytic cycle.