Carbon‐Sulfur Bond Constructions: From Transition‐Metal Catalysis to Sustainable Catalysis

Abstract

The recent decade evidenced a significant development in the construction of the CÀ S bond. The journey began with transitional-metal catalysis and reached sustainable catalysis via oxidant, photo, and electro catalyzed methods. A variety of catalytic systems have been explored for the CÀ S bond formation using a variety of sulfur precursors. This personal account provides an inclusive discussion of these developed methods in terms of reactivity, sustainability and productivity.

Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges

“…For example, thioethers are an important class of organic compounds that have applications in biological chemistry, design of drugs, organic synthesis, and material chemistry. − A brief illustrative overview of a few selected examples of chalcogen-based compounds studied in the areas of drug design, biologically active compounds, agrochemicals, and materials chemistry is provided (Table ). Various aspects have been considered in excellent reviews dedicated to a specific topic. ,,− …”

“…Of course, it should be mentioned that noncatalytic methods were successfully used for a long time for the preparation of organosulfur and other organochalcogen compounds and still are involved in organic synthesis. Just a few representative examples may be mentioned in this regard. ,,,,− We do not consider noncatalytic reactions in this review since we focus only on newly developed catalytic methodologies, which demonstrate a number of advantages and future potential.…”

BF3·OEt2 catalyzed S–H insertion reactions of α-diazo imidamides and enolizable thioamides under metal-free conditions

“…The journey of C–S bond construction has received much attention as sulfur-containing moieties are present in many pharmaceutically important drug molecules, agrochemicals, materials and natural products. 1 C–S bond formation has been generally carried out 2 via the reaction of organic halides/unsaturated C–C bonds with thiols, C–H bond activation and decarboxylative C–S coupling, under free-radical or metal-catalyzed conditions. Additionally, the S–H insertion reactions between diazocarbonyl compounds and thiols through various strategies such as metal catalysis which proceeds through the formation of metal carbenes, 3 organocatalysis, 4 heterogeneous catalysis 5 and photolysis 6 as well as biocatalysis 7 are worth noting.…”

“…A large number of reports have proved that indole derivatives with nitrogen, oxygen or sulfur substitution at the C-2 or C-3 position possess biological activity and they are employed extensively in synthesis as well as in the pharmaceutical industry. 10 For example, the representative indole derivatives I–IV with sulphur substitution at the C-3 position are shown to have biological activity, namely anti-cancer, 10 anti-HIV, 10 COX-2 inhibiting, 1 anti-allergic, 1 or tumour suppressing activity 10 (Fig. 1).…”

Copper-promoted direct sulfenylation of C1–H bonds in 4-aryl pyrrolo[1,2-a]quinoxalines

“…Carbon–sulfur bonds are often found in synthetically and practically useful molecules. 4 While the cross coupling of (pseudo)halides and thiols to afford C–S bonds has been precedented, it suffers from inevitable pre-functionalization. Thus, sulfenylation of C–H bonds would be beneficial from the atom- and step-economy standpoints.…”