Issue 13, 2024

Mechanistic insights into the rhodium catalysed dehydrogenative cycloaddition of cyano-yne-allene substrates

Abstract

The continued progress in creating novel acceptorless dehydrogenations for environmentally friendly and efficient chemical synthesis is anticipated to be significantly shaped by the design of efficient catalysts that can do the job. In this study, we present a comprehensive mechanistic investigation utilizing DFT calculations to elucidate the mechanism of the [RhCl(PPh3)3]-catalysed dehydrogenative cycloaddition of cyano-yne-allene substrates. Overall, the reaction can be described as a cycloaddition involving the three unsaturations, followed by a hydrogen shift, 6π electrocyclization and acceptorless H2 elimination. The crucial factors contributing to the observed reactivity are as follows: (i) the favoured cycloaddition pathway involves the external double bond of the allene in the formation of the initial metallacycle; (ii) the stabilization of the alkyne insertion intermediate that occurs through η3-coordination to the rhodium; and (iii) the presence of a weak base that assists in deprotonation.

Graphical abstract: Mechanistic insights into the rhodium catalysed dehydrogenative cycloaddition of cyano-yne-allene substrates

Supplementary files

Article information

Article type
Research Article
Submitted
27 Feb 2024
Accepted
15 May 2024
First published
16 May 2024
This article is Open Access
Creative Commons BY-NC license

Org. Chem. Front., 2024,11, 3655-3662

Mechanistic insights into the rhodium catalysed dehydrogenative cycloaddition of cyano-yne-allene substrates

À. Díaz-Jiménez, A. Roglans, M. Solà and A. Pla-Quintana, Org. Chem. Front., 2024, 11, 3655 DOI: 10.1039/D4QO00378K

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