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Updated: Jan 9, 2026

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A Nickel/SiH Catalytic Platform for Linear-Selective Reductive 1,2-Hydrovinylation of 1,3-Dienes With Vinyl Triflates
Sheng Wang1, Wen-Yu Wang1, Xiaobo Pang1
1State Key Laboratory of Natural Product Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, China.
Abstract:
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 NiBr2 and a CF3-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.
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