Issue 20, 2023

Computational insights into the dual reactivity of 1,2,3,4-tetrazole: a metalloporphyrin-catalyzed click reaction and denitrogenative annulation

Abstract

The mechanism and origins of chemoselectivities of Mn- and Fe-porphyrin catalyzed click reactions and denitrogenative annulation between 1,2,3,4-tetrazole and phenylacetylene have been studied by performing density functional theory (DFT) calculations. In the Mn-porphyrin-based catalytic system, 1,2,3,4-tetrazole prefers to follow the click reaction pathway to afford a 1,5-disubstituted click product, and the denitrogenation pathway is disfavored by 0.9 kcal mol−1. In contrast, in the Fe-porphyrin-based catalytic system, 1,2,3,4-tetrazole prefers to follow the denitrogenative annulation pathway to afford an annulation product, and the click reaction is disfavored by 15.9 kcal mol−1. The denitrogenative annulation involves the formation of a metal-nitrene radical intermediate by the loss of dinitrogen gas from the metal-azide complex, which is calculated to be the chemoselectivity-determining step. The sluggish dinitrogen elimination in the Mn-catalyzed system may be arising from the destruction of the stable electronic structure of the d-orbital half-filled shell of the Mn-azide complex.

Graphical abstract: Computational insights into the dual reactivity of 1,2,3,4-tetrazole: a metalloporphyrin-catalyzed click reaction and denitrogenative annulation

Supplementary files

Article information

Article type
Research Article
Submitted
24 May 2023
Accepted
26 Jul 2023
First published
27 Jul 2023

Org. Chem. Front., 2023,10, 5055-5063

Computational insights into the dual reactivity of 1,2,3,4-tetrazole: a metalloporphyrin-catalyzed click reaction and denitrogenative annulation

D. Ding, X. Chen, X. Su, Y. She and Y. Yang, Org. Chem. Front., 2023, 10, 5055 DOI: 10.1039/D3QO00777D

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