Department of Chemistry, Indian Institute of Technology Madras, Chennai-600036, Tamil Nadu, India.
Org Biomol Chem. 2021 Feb 25;19(7):1459-1482. doi: 10.1039/d0ob02320e.
Sulfur-containing compounds are present in a wide range of biologically important natural products, drugs, catalysts, and ligands and they have wide applications in material chemistry. Transition metal-catalyzed C-S bond-forming reactions have successfully overcome the obstacles associated with traditional organosulfur compound syntheses such as stoichiometric use of metal-catalysts, catalyst-poisoning and harsh reaction conditions. One of the key demands in metal-catalyzed C-S bond-forming reactions is the use of an appropriate sulfur source due to its odor and availability. The unpleasant odor of many organic sulfur sources might be one of the reasons for the metal-catalyzed C-S bond-forming reactions being less explored compared to other metal-catalyzed C-heteroatom bond-forming reactions. Hence, employing an appropriate sulfur surrogate in the synthesis of organosulfur compounds in metal-catalyzed reactions is still of prime interest for chemists. This review explores the recent advances in C-S bond formation using transition metal-catalyzed cross-coupling reactions and C-H bond functionalization using diverse and commercially available sulfur surrogates. Based on the different transition metal-catalysts, this review has been divided into three major classes namely (1) palladium-catalyzed C-S bond formation, (2) copper-catalyzed C-S bond formation, and (3) other metal-catalyzed C-S bond formation. This review is further arranged based on the different sulfur surrogates. Also, this review provides an insight into the growing opportunities in the construction of complex organosulfur scaffolds covering natural product synthesis and functional materials.
含硫化合物存在于广泛的生物重要天然产物、药物、催化剂和配体中，它们在材料化学中有广泛的应用。过渡金属催化的 C-S 键形成反应成功克服了传统有机硫化合物合成中存在的障碍，例如使用化学计量的金属催化剂、催化剂中毒和苛刻的反应条件。在金属催化的 C-S 键形成反应中，一个关键的需求是使用适当的硫源，因为硫源具有气味和可用性。许多有机硫源的难闻气味可能是与其他金属催化的 C-杂原子键形成反应相比，金属催化的 C-S 键形成反应探索较少的原因之一。因此，在金属催化反应中合成有机硫化合物时，使用适当的硫代试剂仍然是化学家关注的首要问题。本综述探讨了使用过渡金属催化交叉偶联反应形成 C-S 键和使用各种商业可得的硫代试剂进行 C-H 键功能化的最新进展。基于不同的过渡金属催化剂，本综述分为三大类，即（1）钯催化的 C-S 键形成，（2）铜催化的 C-S 键形成，和（3）其他金属催化的 C-S 键形成。本综述还根据不同的硫代试剂进行了安排。此外，本综述深入探讨了在构建复杂有机硫骨架方面的新机遇，包括天然产物合成和功能材料。
