Group 14 Elements Hetero‐Difunctionalizations via Nickel‐Catalyzed Electroreductive Cross‐Coupling

The difunctionalization of unsaturated bonds plays a vital role in the enrichment of molecular complexity. While various catalytic methods for alkene and alkyne difunctionalization have been developed in recent years, hetero‐functionalization the introduction of two different atoms has been less explored. This is mainly due to the challenges associated with achieving high chemo‐, regio‐, and stereoselectivity, especially when adding two similar atoms from the same group across unsaturated bonds. In this study, we describe a nickel‐catalyzed, three‐component reductive protocol for group 14 element hetero‐difunctionalization of 1,3‐enynes using electrochemistry. This new method is mild, selective, and general, allowing for the silyl‐, germanyl‐, and stannyl‐alkylation of enynes. Various chlorosilanes as well as chlorogermans, and chlorostannanes can be successfully used in combination with aryl/alkyl‐substituted 1,3‐enynes and primary, secondary, and tertiary alkyl bromides in the electroreductive coupling. A nickel‐catalyzed three‐component reductive protocol for hetero‐difunctionalization with group 14 elements via electrochemistry is described. The cascade reaction proceeded smoothly with the diverse chlorosilanes, 1,3‐enynes, primary, secondary, and tertiary alkyl bromides. Good chemo‐ and regioselectivities were achieved. This protocol could be extended to germanyl‐ and stannylalkylation of 1,3‐enynes, showing its generality and versatility.