Issue 14, 2023

Mechanisms and origin of regioselectivity for manganese-catalyzed denitrogenative annulation and click reactions

Abstract

This paper presents a density functional theory study concerning the mechanisms and origin of regioselectivity associated with a Mn-catalyzed denitrogenative annulation involving benzonitrile as the substrate and a click reaction with phenylacetylene as the substrate, respectively. These calculations fully addressed multi-spin-state reactivity. The catalytic cycle for the Mn-catalyzed denitrogenative annulation was found to involve tetrazole ring opening followed by N2 elimination and the formation of C–N and N–N bonds. The proposed catalytic cycle for the Mn-catalyzed click reaction involves three stages: tetrazole ring opening, isomerization and 1,3-cycloaddition. A manganese-copper/zinc cooperative mechanism is proposed to account for experimental results. CuI promotes C–N bond formation between the benzonitrile and Mn-nitrene, promoting the predominant formation of the 1,2,4-triazolo-pyridine. An analysis of the click reaction using the distortion/interaction model indicated that distortion energy plays the primary role in determining regioselectivity.

Graphical abstract: Mechanisms and origin of regioselectivity for manganese-catalyzed denitrogenative annulation and click reactions

Supplementary files

Article information

Article type
Research Article
Submitted
20 Mar 2023
Accepted
10 Jun 2023
First published
13 Jun 2023

Org. Chem. Front., 2023,10, 3642-3653

Mechanisms and origin of regioselectivity for manganese-catalyzed denitrogenative annulation and click reactions

G. Song, W. Rong, Y. Liu and J. Li, Org. Chem. Front., 2023, 10, 3642 DOI: 10.1039/D3QO00406F

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