A Nickel/SiH Catalytic Platform for Linear‐Selective Reductive 1,2‐Hydrovinylation of 1,3‐Dienes With Vinyl Triflates

Reductive hydrofunctionalization of 1,3‐dienes by transition‐metal/SiH catalysis has emerged as a promising strategy for the rapid construction of molecular complexity from simple precursors. However, previous reports have predominantly focused on branched‐selective 1,2‐hydrofunctionalization pathways. Herein, we describe a reductive 1,2‐hydrovinylation of 1,3‐dienes with vinyl triflates that proceeds with exclusive linear selectivity. This transformation establishes a new selectivity paradigm in transition‐metal/SiH catalysis, wherein a Ni–C insertion pathway overrides the classical Ni–H insertion process, enabled by the synergistic cooperation between NiBr 2 and a CF 3 ‐substituted PyrOX ligand. The reaction features a broad substrate scope, encompassing a wide range of aryl and heteroaryl 1,3‐dienes as well as both cyclic and acyclic vinyl triflates.