Issue 37, 2022

A dinickel-catalyzed three-component cycloaddition of vinylidenes

Abstract

A dinickel catalyst promotes the [2 + 2 + 1]-cycloaddition of two aldehyde equivalents and a vinylidene. The resulting methylenedioxolane products can be deprotected in one pot under acidic conditions to reveal α-hydroxy ketones. This method provides convenient access to unsymmetrical alkyl-substituted α-hydroxy ketones, which are challenging to synthesize selectively using cross-benzoin reactions. Mechanistic studies are consistent with an initial migratory insertion of the aldehyde into a dinickel bridging vinylidene. Insertion of the second aldehyde followed by C–O reductive elimination furnishes the cycloadduct. Under dilute conditions, an enone side product is generated due to a competing β-hydride elimination from the proposed metallacyclic intermediate. A DFT model consistent with the concentration-dependent formation of the methylenedioxolane and enone is presented.

Graphical abstract: A dinickel-catalyzed three-component cycloaddition of vinylidenes

Supplementary files

Article information

Article type
Edge Article
Submitted
14 May 2022
Accepted
17 Aug 2022
First published
08 Sep 2022
This article is Open Access

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

Chem. Sci., 2022,13, 11190-11196

A dinickel-catalyzed three-component cycloaddition of vinylidenes

A. E. Kalb, M. Liu, M. I. Bosso and C. Uyeda, Chem. Sci., 2022, 13, 11190 DOI: 10.1039/D2SC02696A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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