An efficient and simple synthesis of 1-thiocarbamoylindoles is reported in which 1H-indoles react with tetramethylthiuram monosulfide (TMTM) to give a series of 1-thiocarbamoylindoles that were obtained­ in good to excellent yields. The procedure was promoted by Cs2CO3 under transition-metal-free conditions and gives a simple entry to protected indoles.

A simple and efficient synthetic method to C−S bonds was established based on the Chan–Lam reaction. A series of O/N‐alkyl S‐phenyl phenylcarbamothioates were obtained in good yields by using odorless O/N‐alkyl phenylthiocarbamates as sulfur sources and commercially available phenylboronic acids as substrates catalyzed by Cu(OAc)2. This methodology features simple performance, odorless sulfur source, easily available starting material, good functional group tolerance, and high chemo‐selectivity to construct C−S bonds, thereby providing an alternative way to the synthesis of potentially bioactive compounds.