Three‐Component Synthesis of 2‐Substituted Thiobenzoazoles Using Tetramethyl Thiuram Monosulfide (TMTM) as Thiocarbonyl Surrogate

Abstract

A metal‐free synthesis of 2‐benzyl/allyl‐substituted thiobenzoazoles was developed starting from tetramethyl thiuram monosulfide (TMTM) which served as thiocarbonyl surrogate. By using 2‐aminophenols (or 2‐aminothiophenols, or 1,2‐phenylenediamines) and TMTM as starting materials, 2‐mercaptobenzoazoles could be synthesized efficiently. The subsequent C–S bond formation with benzyl/allyl halides gave the final products (2‐benzyl/allyl‐substituted thiobenzoazoles) with good to excellent yields. The metal‐free conditions, inexpensive and easily available starting materials, and broad substrate scope are the advantageous features of this protocol.

One-Pot Synthesis of Benzoazole-Substituted Thioenamines via a Cross Dehydrogenation Coupling (CDC) Reaction

“…Recently, some new strategies were reported, such as biocatalysis, graphene oxide promotion, and visible light induction, which match the merits of green chemistry. As part of our long-term interest in developing sulfur-containing compounds based on C–S bond formation reactions and inspired by the organic reactions promoted by molecular iodine, we herein report an iodine-catalyzed one-pot synthesis of benzoazole-substituted thioenamines, which further expands our previously reported organosulfur chemistry based on green synthesis …”

Selective Csp3–F Bond Functionalization with Lithium Iodide

“…The spectroscopic data of 2-((4-nitrobenzyl)thio)benzo[d]oxazole (29) are in accordance with the literature. 65 1 H NMR (400 MHz, chloroform-d):  = 8.16 (dd, J = 6.8, 2.0 Hz, 2 H), 7.63 (dd, J = 6.8, 2.0 Hz, 2 H), 7.59 (dd, J = 7.5, 1.6 Hz, 1 H), 7.42 (dd, J = 7.5, 1.6 Hz, 1 H), 7.32-7.19 (m, 2 H), 4.58 (s, 2 H). 13 C NMR (100 MHz, chloroform-d):  = 163.…”

“…The spectroscopic data of 4-((benzo[d]oxazol-2-ylthio)methyl)benzonitrile (31) are in accordance with the literature. 65 1 H NMR (400 MHz, chloroform-d):  = 7.64-7.54 (m, 5 H), 7.41 (dd, J = 7.5, 1.6 Hz, 1 H), 7.31-7.20 (m, 2 H), 4.54 (s, 2 H). 13 C NMR (100 MHz, chloroform-d):  = 163.6, 152.1, 142.0, 141.7, 132.6, 129.9, 124.…”

Synthesis of Diaryl Sulfides by Using Tetramethylthiuram Monosulfide (TMTM) as Organosulfur Source: A Practical C(sp2)−S Bond Construction

“…In addition, this sulfidation reagent can preferentially generate monosulfur structures to affect the sulfidation rate and efficiency, and ultimately promote the progress of the sulfidation reaction [23] . We previously reported the synthesis of benzoxazoles using the thiocarbonyl moiety of tetramethylthiuram monosulfide [21c] (Scheme 1d). Herein, we would like to report a protocol for the construction of symmetrical phenyl sulfides using the monosulfur moiety in TMTM which could be an easily available and cheap sulfur source (Scheme 1e).…”