Regiocontrolled Reductive Vinylation of Aliphatic 1,3-Dienes with Vinyl Triflates by Nickel Catalysis

The regiocontrolled functionalization of 1,3-dienes has become a powerful tool for divergent synthesis, yet it remains a long-standing challenge for aliphatic substrates. Herein, we report a reductive approach for a branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R-X electrophiles, which represents a new selectivity pattern for diene functionalization. Simple butadiene, aromatic 1,3-dienes, and highly conjugated polyene were also tolerated. The combination of Ni(0) and the phosphine-nitrile ligand generally resulted in >20:1 regioselectivity with the retention of the geometry of the C3-C4 double bonds. This reaction proceeds with a broad substrate scope, and it allows for the conjugation of two biologically active units to form more complex polyene molecules, such as tetraene and pentaene as well as heptaene.

Automated summary

A reductive approach for branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R-X electrophiles is reported in this study, showing a new selectivity pattern for diene functionalization. The combination of Ni(0) and the phosphine-nitrile ligand resulted in >20:1 regioselectivity, allowing for the conjugation of two biologically active units to form more complex polyene molecules.