Issue 42, 2021

Ligand-redox assisted nickel catalysis toward stereoselective synthesis of (n+1)-membered cycloalkanes from 1,n-diols with methyl ketones

Abstract

A well-defined, bench-stable nickel catalyst is presented here, that can facilitate double alkylation of a methyl ketone to realize a wide variety of cycloalkanes. The performance of the catalyst depends on the ligand redox process comprising an azo-hydrazo couple. The source of the bis electrophile in this double alkylation is a 1,n-diol, so that (n+1)-membered cycloalkanes can be furnished in a stereoselective manner. The reaction follows a cascade of dehydrogenation/hydrogenation reactions and adopts a borrowing hydrogen (BH) method. A thorough mechanistic analysis including the interception of key radical intermediates and DFT calculations supports the ligand radical-mediated dehydrogenation and hydrogenation reactions, which is quite rare in BH chemistry. In particular, this radical-promoted hydrogenation is distinctly different from conventional hydrogenations involving a metal hydride and complementary to the ubiquitous two-electron driven dehydrogenation/hydrogenation reactions.

Graphical abstract: Ligand-redox assisted nickel catalysis toward stereoselective synthesis of (n+1)-membered cycloalkanes from 1,n-diols with methyl ketones

Supplementary files

Article information

Article type
Edge Article
Submitted
04 8 2021
Accepted
04 10 2021
First published
05 10 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 14217-14223

Ligand-redox assisted nickel catalysis toward stereoselective synthesis of (n+1)-membered cycloalkanes from 1,n-diols with methyl ketones

A. K. Bains, A. Kundu, D. Maiti and D. Adhikari, Chem. Sci., 2021, 12, 14217 DOI: 10.1039/D1SC04261K

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