Transition‐Metal‐Free C(sp3)–S Coupling in Water: Synthesis of Benzyl Dithiocarbamates Using Thiuram Disulfides as an Organosulfur Source.

A simple, highly efficient and environmentally benign method for the synthesis of benzyl dithiocarbamates was reported. Without addition of metal catalyst, a series of 34 benzyl dithiocarbamates were obtained in good to excellent yields by treating benzyl halides with tetraalkylthiuram disulfides in water. The protocol allows easy access to C(sp3)–S bond formation, features the advantages of easy performance, environmental friendliness, good to excellent yields, and good functional tolerance, showing potential value for the preparation of some biologically active compounds. By the treatment of benzyl halides with tetraalkylthiuram disulfides (TMTD, TETD and TBTD), the desired C(sp3)‐S coupling products (benzyl dithiocarbamates) could be obtained in good to excellent yields. The protocol features advantages of experimental simplicity, water as solvent, metal‐free, good functional compatibility, good to excellent yields, illustrating its potential synthetic value in the convenient preparation of some potentially biologically active compounds. [ABSTRACT FROM AUTHOR]