Thione–Thiol Rearrangement: Miyazaki–Newman–Kwart Rearrangement and Others

Abstract

Thione-to-thiol rearrangements represent a general route for the synthesis of sulfur compoundsfrom hydroxyl functionalities. In particular, the Miyazaki-Newman-Kwart rearrangementhas been widely used for the synthesis of aromatic thiols from the corresponding phenols.

Polymers and Sulfur: what are Organic Polysulfides Good For? Preparative Strategies and Biological Applications

“…It is noteworthy that they can be produced efficiently through thione‐thiol rearrangements. Specifically, the Miyazaki‐Newman‐Kwart rearrangements129 (Scheme ), where X = N are of interest due to their regiospecificity, since the nitrogen‐linked groups are not involved in any positional rearrangement (while, when X = O, R and R′ may exchange places).…”

Microwave-mediated Newman–Kwart rearrangement in water

“…2 and 3). The reactions with cucurbit [6]uril 8 and SC6C3 7a resulted in hardly increased conversions of 43% and 45%, respectively, whereas the employment of SC8C8 7b gave an 21% improvement versus the rearrangement without additive. As described above, at elevated temperatures water acts as pseudoorganic solvent and is able to dissolve non-polar substrates.…”

“…[1][2][3] In light of the easy availability of various phenols 1, their facile conversion to N,N-dimethyl O-arylthiocarbamates 2 as well as the readily achieved cleavage of the NKR product 3 by hydrolysis, methanolysis, or reduction, the NKR is one of the most synthetically attractive routes for the formation of thiophenols 4 from phenols 1 (Scheme 1). [4][5][6] Both thiophenols and similarly accessible sulfur-containing compounds such as sulfoxides, sulfones, thioethers, and sulfonic acids contribute to a broad eld of applications including agrochemicals, dyestuffs, medicinal chemistry, chiral ligands, molecular switches, organocatalysts, dendrimers and supramolecular assemblies. [5][6][7] Not least, the NKR can be utilized for the synthesis of specic arenes from phenols 1 by desulfurization of the corresponding thiophenols 4.…”

“…[4][5][6] Both thiophenols and similarly accessible sulfur-containing compounds such as sulfoxides, sulfones, thioethers, and sulfonic acids contribute to a broad eld of applications including agrochemicals, dyestuffs, medicinal chemistry, chiral ligands, molecular switches, organocatalysts, dendrimers and supramolecular assemblies. [5][6][7] Not least, the NKR can be utilized for the synthesis of specic arenes from phenols 1 by desulfurization of the corresponding thiophenols 4.…”

“…3), i.e. cucurbit [6]uril, imidazolio-and sulfocalix[n]arenes, and nally, a more in-depth kinetic study of 2and 4-nitrophenyl O-thiocarbamate investigating the effect of water in terms of a possible transition state 5 stabilization.…”