Ligand-Controlled Ni-Catalyzed Regiodivergent Hydrocyanation of Unactivated Alkynes toward Linear and Branched Vinyl Nitriles

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2896 - 2903

Published: Feb. 3, 2025

Language: Английский

Regioselective Hydrocyanation of Internal Alkynes Enabled by a Transition‐Metal‐Free Dual‐Catalytic System

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: April 27, 2025

Abstract Since its discovery in 1954, the hydrocyanation of multiple carbon‐carbon bonds has emerged as a powerful strategy for synthesis nitriles. However, elusive control selectivity and typical reliance on expensive toxic transition metal (TM) based catalysts significantly hinder utility this process. Here, we report an exclusively regioselective unbiased alkynes, driven by base‐catalyzed reversible alkyne‐allene isomerization phosphine‐catalyzed HCN transfer to allene. This TM‐free, dual‐catalytic approach introduces novel mode via allene intermediate. The methodology secures cost‐effective access broad range vinyl nitriles (40 examples) with yields up 97% Z/E stereoselectivity 20:1, including complex natural product derivatives. A comparison TM‐based systems highlighted 2500‐fold cost reduction, well elimination troublesome separation regioisomers. Mechanistic studies elucidated reaction pathway, shedding light achieved regioselectivity. By altering one catalyst system, demonstrated regioselectivity switch, thereby facilitating regiodivergent (eight examples). In broader context, offers foundation developing next generation TM‐free strategies hydrofunctionalizations alkynes.

Language: Английский

Formal 1,1-Hydrocyanation Reaction of Alkynyl Halides with Isocyanides Enabled by Dual Nickel/Base Catalysis Relay

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

We herein describe a formal 1,1-hydrocyanation reaction of alkynyl halides with isocyanides enabled by dual nickel/base catalysis relay.

Language: Английский