Work

A General Catalyzed Cyanation of Aryl Bromides and Hydrocyanation of Olefins Using Acetonitrile as Cyanide Surrogate

Year: 2025

Type: preprint

Abstract: Traditional methods for nitrile synthesis often rely on toxic cyanide reagents, raising serious safety and environmental concerns. Under mild conditions, acetonitrile, a bench-stable and cyano-containing solvent, has emerged as a promising cyanide source for nitrile construction. Herein, we report a highly efficient photoredox nickel dual catalytic system for the cyanation of aryl bromides and the hydrocyanation of olefins, employing acetonitrile as a cyanide surrogate under visible-light irradiation. The mechanism was elucidated through the synthesis and characterization of key nickel intermediates. These studies support a transmetalation process between Ni-CN and Ni-Ar species to generate a mixed Ar-Ni-CN complex, which undergoes reductive elimination to form the aryl nitrile. Furthermore, the protocol enables the synthesis of both linear and branched aliphatic nitriles from a wide range of olefins, including terminal and internal alkenes.

Source: ChemRxiv

DOI: 10.26434/chemrxiv-2025-0r8bn

Authors: Jingjing Meng, Suyun Sun, Sergi Danés, Mattia Vettori, Sergio Fernández, Julio Lloret-Fillol

Institutions: Institut Català d'Investigació Química, Barcelona Institute of Science and Technology, Universitat Rovira i Virgili, Institució Catalana de Recerca i Estudis Avançats

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green