A Single Terminal [NiII-OH] Catalyst for Direct Julia-Type Olefination and α-Alkylation Involving Sulfones and Alcohols

Prabhakar K Pandey; Moumita Patra; Prabodh Ranjan; Nilay Kumar Pal; Sanjay Choudhary; Jitendra K Bera

doi:10.1002/chem.202400337

A Single Terminal [NiII-OH] Catalyst for Direct Julia-Type Olefination and α-Alkylation Involving Sulfones and Alcohols

Chemistry. 2024 Apr 21:e202400337. doi: 10.1002/chem.202400337. Online ahead of print.

Authors

Prabhakar K Pandey¹, Moumita Patra¹, Prabodh Ranjan¹, Nilay Kumar Pal¹, Sanjay Choudhary¹, Jitendra K Bera²

Affiliations

¹ Indian Institute of Technology Kanpur, Chemistry, Kalyanpur, Kanpur, 208016, Kanpur, INDIA.
² Indian Institute of Technology Kanpur, Department of Chemistry, IIT Kanpur, 2018016, Kanpur, INDIA.

PMID: 38644351
DOI: 10.1002/chem.202400337

Abstract

A terminal [NiII-OH] complex 1, supported by triflamide-functionalized NHC ligands, showed divergent reactivity for the reaction of sulfone with alcohol, contingent on base concentration, temperature, and time. Julia-type olefination of alcohols with sulfones was achieved using one equiv. of base, whereas lowering base loading to 0.5 equiv. afforded α-alkylated sulfones. Besides excellent substrate scope and selectivity, biologically active stilbene derivatives DMU-212, pinosylvin, resveratrol, and piceatannol were synthesized in high yield under Julia-type olefination conditions. An extensive array of controlled experiments and DFT calculations provide valuable insight on the reaction pathway.

Keywords: nickel * olefination * α-alkylation * borrowing-hydrogenation * stilbene.