Rhodium-Catalyzed Alkyne Hydrothiolation with Aromatic and Aliphatic Thiols

Citations Over TimeTop 10% of 2005 papers

Abstract

Alkyne hydrothiolation is a potentially attractive method for the formation of vinyl sulfides, which are valuable synthetic intermediates. Known methods for hydrothiolation using alkyl thiols are quite limited. We report herein that Tp*Rh(PPh3)2 (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) is a highly active catalyst for alkyne hydrothiolation with alkyl and aryl thiols. Hydrothiolation using alkyl thiols proceeds with excellent regioselectivity, providing convenient access to branched alkyl vinyl sulfides, which are difficult to synthesize by other means. A mixture of regioisomers is obtained when using aryl thiols, with the branched isomer as the major product, opposite that reported for other Rh complexes.

Related Papers

• → Electronic and Steric Effects Control Regioselectivity in Alkyne Migratory Insertion during Ni-Catalyzed Indenone Synthesis(2023)4 cited
• → Formation of alkyl (or aryl) chlorosilanes by the direct reaction of alkyl (or aryl) chlorides with silicon(1962)
• → Formation of alkyl(aryl)chlorosilanes in the direct reaction of alkyl(aryl)chlorides with silicon(1970)