Issue 3, 2019

Copper(i)-carbenes as key intermediates in the [3 + 2]-cyclization of pyridine derivatives with alkenyldiazoacetates: a computational study

Abstract

This work reports a computational study of the copper(I)-catalyzed regioselective synthesis of indolizine derivatives through the [3 + 2]-cyclization reaction of vinyldiazo acetates and pyridine derivatives. This reaction is predicted to proceed via a multi-step process with the initial decomposition of the diazo function and generation of an electrophilic copper(I) carbene intermediate. Subsequent attack of the pyridine derivative at the vinylogous position of the carbene would generate a vinylcuprate intermediate that would evolve to the final products through a sequence involving cyclization, reductive elimination, metal decoordination and final oxidative aromatization. According to our calculations, an alternative pathway involving the initial activation of the pyridine seems unlikely. These theoretical results could pave the way for further developments in vinyldiazo chemistry.

Graphical abstract: Copper(i)-carbenes as key intermediates in the [3 + 2]-cyclization of pyridine derivatives with alkenyldiazoacetates: a computational study

Supplementary files

Article information

Article type
Paper
Submitted
29 okt 2018
Accepted
14 dek 2018
First published
14 dek 2018

Org. Biomol. Chem., 2019,17, 646-654

Copper(I)-carbenes as key intermediates in the [3 + 2]-cyclization of pyridine derivatives with alkenyldiazoacetates: a computational study

L. A. López and J. González, Org. Biomol. Chem., 2019, 17, 646 DOI: 10.1039/C8OB02676A

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