Photoinduced carbamoylation reactions: unlocking new reactivities towards amide synthesis

Author(s)

Matsuo, Bianca T. ; Oliveira, Pedro H. R. ; Pissinati, Emanuele F. ; Vega, Kimberly B. ; de Jesus, Iva S. ; Correia, Jose Tiago M. ; Paixao, Marcio

• Document type: Journal article
• Source: CHEMICAL COMMUNICATIONS; v. 58, n. 60, p. 18-pg., 2022-07-07.

Abstract

The preparation of amide-containing compounds is among the most interesting and challenging topics for the synthetic community. Such relevance is given by their reactive aspects explored in the context of organic synthesis and by the direct application of these compounds as pharmaceuticals and useful materials, and their key roles in biological structures. A simple and straightforward strategy for the amide moiety installation is the use of carbamoyl radicals - this nucleophilic one-electron intermediate is prone to undergo a series of transformations, providing a range of structurally relevant derivatives. In this review, we summarize the latest advances in the field from the perspective of photoinduced protocols. To this end, their synthetic applications are organized accordingly to the nature of the radical precursor (formamides through HAT, 4-substituted-1,4-dihydropyridines, oxamic acids, and N-hydroxyphthalimido esters), the mechanistic aspects also being highlighted. The discussion also includes a recent approach proceeding via photolytic C-S cleavage of dithiocarbamate-carbamoyl intermediates. By exploring fundamental concepts, this material aims to offer an understanding of the topic, which will encourage and facilitate the design of new synthetic strategies applying the carbamoyl radical. (AU)

• FAPESP's process: 21/06099-5 - Development of new photochemical methodologies for the synthesis of small molecule and biomolecule modifications
• Grantee: Márcio Weber Paixão
• Support Opportunities: Regular Research Grants
• FAPESP's process: 17/10015-6 - Photocatalysis Applied to the Synthesis of N-heterocycles: New Strategies for Intercepting Radical Intermediates Generated in Processes Promoted by Visible-light-Tris (trimethylsilyl)silane Combination.
• Grantee: José Tiago Menezes Correia
• Support Opportunities: Scholarships in Brazil - Post-Doctoral