Department of Chemistry, Federal University of São Carlos, Rodovia Washington Luís, km 235 - SP-310 - São Carlos, São Paulo, 13565-905, Brazil.
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104-6323, USA.
Chem Commun (Camb). 2022 Jul 26;58(60):8322-8339. doi: 10.1039/d2cc02585j.
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 -hydroxyphthalimido esters), the mechanistic aspects also being highlighted. The discussion also includes a recent approach proceeding 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.
酰胺类化合物的制备是合成领域最有趣和最具挑战性的课题之一。它们在有机合成中的反应性以及作为药物和有用材料的直接应用，以及它们在生物结构中的关键作用，赋予了它们这种相关性。在酰胺部分的安装中，使用氨甲酰自由基是一种简单直接的策略——这种亲核单电子中间体能经历一系列转化，提供一系列结构相关的衍生物。在这篇综述中，我们从光诱导方案的角度总结了该领域的最新进展。为此，根据自由基前体的性质（通过 HAT 的甲酰胺、4-取代的 1,4-二氢吡啶、氨基甲酸、-羟基邻苯二甲酰亚胺酯）对其合成应用进行了组织，还强调了其机械方面。讨论还包括最近一种通过光解二硫代氨基甲酸酯-氨甲酰中间体进行 C-S 断裂的方法。通过探索基本概念，本材料旨在提供对该主题的理解，这将鼓励和促进应用氨甲酰自由基的新合成策略的设计。
