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 Aug 2021
Accepted
04 Oct 2021
First published
05 Oct 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

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements