Tandem Acceptorless Dehydrogenative Coupling–Decyanation under Nickel Catalysis

Abstract

The development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented CC bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.

Olefins from alcohols via catalytic acceptorless dehydrogenation coupling reactions

“…Synthesis of α,β-unsaturated ketone using alcohol α,β-Unsaturated ketones have broad applications in the synthesis of pharmaceuticals, biologically active compounds, Scheme 19 Ni-NNN complex catalyzed decyanative olefination of nitriles using alcohol. 46 Scheme 20 Plausible catalytic cycle for Ni-NNN complex catalyzed decyanative olefination of nitriles using alcohol.…”

“…In 2021, Balaraman and co-workers disclosed an unprecedented olefin ( E ) synthesis using nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles via a decyanation pathway, 46 where previous reports had shown α-alkylated/alkenylated products with the same starting materials. After screening several reaction conditions, the optimization experiments revealed that 4-methoxybenzyl alcohol and 2-phenylacetonitrile underwent a Ni-catalyzed (Cat.…”

Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

“…The olefination of alcohols using Wittig alkenylation, sulfones or via dehydrogenative decyanation reaction of cyanide was also performed by various groups for the regioselective synthesis of olefinated products 158-160 (Scheme 67). [126][127][128] An attempt for the synthesis of resveratrol (3,5,4 0 -trihydroxy-trans-stilbene), 129 was also successful. Resveratrol is a phytoalexin that inhibits the growth of bacteria and fungus.…”

Recent advances in C/N-alkylation with alcohols through hydride transfer strategies

“…The unprecedented report of a nickel catalyzed dehydrogenative–decynative coupling of alcohols with nitriles to establish E-olefins was published recently by Balaraman's research group (Scheme 41a). 52 Various primary and secondary alcohols were employed in combination with benzylcyanide derivatives under optimized reaction conditions. Electron withdrawing groups decreased the yield of the reaction.…”