Rhodium-Catalyzed Synthesis of Organosulfur Compounds Involving S-S Bond Cleavage of Disulfides and Sulfur

Abstract

Organosulfur compounds are widely used for the manufacture of drugs and materials, and their synthesis in general conventionally employs nucleophilic substitution reactions of thiolate anions formed from thiols and bases. To synthesize advanced functional organosulfur compounds, development of novel synthetic methods is an important task. We have been studying the synthesis of organosulfur compounds by transition-metal catalysis using disulfides and sulfur, which are easier to handle and less odiferous than thiols. In this article, we describe our development that rhodium complexes efficiently catalyze the cleavage of S-S bonds and transfer organothio groups to organic compounds, which provide diverse organosulfur compounds. The synthesis does not require use of bases or organometallic reagents; furthermore, it is reversible, involving chemical equilibria and interconversion reactions.

Copper-Catalyzed Cycloaddition of Heterobicyclic Alkenes with Diaryl Disulfides to Synthesize Dihydrobenzo[b]thiophene Derivatives

“…However, most thiols are air-sensitive and have rank odors, which impede their application. Unlike mercaptans, disulfides are air-stable and odorless sulfur sources and have been used as convenient precursors to introduce sulfur atoms into organic molecules . Especially, transition-metal-catalyzed cleavage of the S–S bond of a disulfide has emerged as a reliable and powerful strategy for constructing sulfur-containing compounds .…”

Continuous Synthesis of N-Cyclohexyl-2-benzothiazole Sulfenamide with Microfluidics and Its Kinetic Study

“…Organosulfur compounds are of considerable interest as important intermediates and reactants in organic synthesis, material chemistry, and biological and pharmaceutical applications. , For example, sulfenamides containing sulfur–nitrogen (S–N) bonds have been commonly used in the synthesis of fine chemicals such as germicides and accelerators for rubber vulcanization . The formation of the S–N bond, referred to as an oxidative coupling reaction, has attracted much attention in the fields of organic synthesis. , Compared with the coupling reactions of hydrocarbons containing C–C and C–Het (Het = N, O, P, and S) bonds, oxidative coupling with S–N bond formation has been much less studied.…”

Organosulphur and organoselenium compounds as emerging building blocks for catalytic systems forO-arylation of phenols, a C–O coupling reaction

“…135 Organosulphur compounds can be synthesized easily using simple and straightforward reaction protocols. 77,[137][138][139][140] However, they (e.g., thiophenol, a very commonly used precursor) are poisonous and foul-smelling in many cases. The use of elemental sulphur is also very prevalent, as it is inexpensive and available in large quantities, 141 and in general its smell is weaker than that of other heteroatom reagents often used, such as thiols.…”