Copper‐Catalyzed S‐Arylation Starting from Arylboronic Acids and Tetraalkylthiuram Disulfide

Abstract

A convenient and useful protocol for the synthesis of diverse S‐aryl dithiocarbamates was studied. Starting from arylboronic acid and tetraalkylthiuram disulfide, copper‐catalyzed C–S coupling proceeds smoothly to give the desired S‐aryl dithiocarbamates in good to excellent yields. The broad substrate scope, short reaction time, easy performance, cheap substrates, and nice yields make this approach attractive, showing its practical synthetic value for the preparation of some biologically or pharmaceutically active compounds.

An Efficient Copper-Catalyzed C(sp2)–S Formation Starting from Aryl Iodides and Tetramethylthiuram Monosulfide (TMTM)

“…12 However, the previously reported methods suffer from complicated reaction conditions, not easy operations, and toxic reaction starting materials, high reaction temperatures, or multiple reaction steps. Recently, our group also reported some referable works, such as reactions between tetramethylthiuram disulfide (TMTD) and arylboronic acids 13 or aryl iodides (Scheme 1). 14 Following this work, and due to our research interests in organosulfur chemistry, 13,15 we herein report an alternative method to achieve the efficient synthesis of phenyl dithiocarbamates by using tetramethylthiuram monosulfide (TMTM), which would be a supplement to our long-term development of thiuram chemistry.…”

“…Recently, our group also reported some referable works, such as reactions between tetramethylthiuram disulfide (TMTD) and arylboronic acids 13 or aryl iodides (Scheme 1). 14 Following this work, and due to our research interests in organosulfur chemistry, 13,15 we herein report an alternative method to achieve the efficient synthesis of phenyl dithiocarbamates by using tetramethylthiuram monosulfide (TMTM), which would be a supplement to our long-term development of thiuram chemistry. 16 The desired products were obtained in high yields under optimal conditions and this protocol proved to be useful and attractive in C-S bond formation.…”

“…1 H NMR (400 MHz, CDCl 3 ):  = 7.28 (d, J = 4.0 Hz, 1 H), 7.26 (d, J = 4.0 Hz, 1 H), 6.87 (d, J = 4.0 Hz, 1 H), 6.85 (d, J = 4.0 Hz, 1 H), 3.71 (s, 3 H), 342 (s, 3 H), 3.34 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ):  = 198. 5,161.1,138.5,122.6,114.8,55.4,45.8,42.0.…”

“…1 H NMR (400 MHz, CDCl 3 ):  = 7.24-7.20 (m, 1 H), 7.14-7.11 (m, 2 H), 3.44 (s, 3 H), 3.37 (s, 3 H). 13…”

“…1 H NMR (400 MHz, CDCl 3 ):  = 7.68 (t, J = 4.0 Hz, 1 H), 7.55-7.46 (m, 3 H), 3.41 (s, 3 H), 3.38 (s, 3 H). 13 C NMR (100 MHz, CDCl 3 ):  = 195.8, 141.6, 133.9 (q, J = 300 Hz), 132.3, 130. 5, 130.4, 126.9…”