Laboratory of Polymers and Catalysis (LaPoCa), Department of Chemistry, Federal University of Paraná - UFPR, P. O. Box 19061, 81531-980, Curitiba, PR, Brazil.
Instituto de Química, Departamento de Química Orgânica, Universidade Federal do Rio Grande do Sul - UFRGS, 91501-970, Porto Alegre, RS, Brazil.
Org Biomol Chem. 2022 Aug 10;20(31):6072-6177. doi: 10.1039/d2ob00986b.
Transition metal catalysed direct sulfanylations of unreactive C-H bonds have become a unique and straightforward synthetic strategy in late-stage C-S bond formation of relevant complex molecules. Such transformations represent a breakthrough in modern synthetic organic chemistry, as they offer unusual reactivity patterns and avoid pre-functionalization of the starting materials. Despite inherent challenges in activating/functionalizing unreactive C-H bonds, a considerable number of different transition metals have shown the ability to selectively catalyze these processes toward C-S bond formation. In this sense, this review article covers the development and mechanistic analysis of the direct sulfanylation of Csp-H and Csp-H bonds through transition metal catalysed reactions in the last two decades, providing an essential guide for organic chemists working on this research area.
过渡金属催化的惰性 C-H 键直接硫代反应在相关复杂分子的晚期 C-S 键形成中已成为一种独特而直接的合成策略。这些转化代表了现代合成有机化学的突破,因为它们提供了不寻常的反应性模式,并避免了起始材料的预官能化。尽管在激活/官能化惰性 C-H 键方面存在固有挑战,但相当多的不同过渡金属已显示出选择性催化这些过程形成 C-S 键的能力。从这个意义上说,本文综述了过去二十年中通过过渡金属催化反应实现 Csp-H 和 Csp-H 键直接硫代反应的发展和机理分析,为从事该研究领域的有机化学家提供了重要指导。