Design, Synthesis, and Applications of ortho -Sulfur Substituted Arylphosphanes

Electrochemical phosphorothiolation and 1,4-S → C phospho-Fries rearrangement: controlled access to phosphorothiolated and mercapto-phosphono substituted indolizines

“…On the basis of the aforementioned results and the literature reports, 6,7 two plausible reaction mechanisms for the electrochemical phosphorothiolation and 1,4-S → C phospho-Fries rearrangement have been depicted in Scheme 8. For the formation of the phosphorothiolation product 3a , Br 2 was first generated via electrochemical oxidization at the anode.…”

“…6 Since elemental sulfur (S 8 ) is low toxic, cheap, and abundant, utilizing it as a sulfur source for the construction of the C–S–P(O) unit proved to be an attractive protocol (Scheme 1c). 7 Tang and Zhao reported the pioneering three-component reactions of arylboronic acids/diaryliodonium/diazonium salts/ N -alkoxypyridinium salts/sulfonamides, elemental sulfur, and H-phosphonates to afford aryl phosphorothioates. 8 Very recently, an electrochemically regioselective C–H phosphorothiolation of (hetero)arenes with NH 4 SCN as the S source under ultrasonic irradiation has been developed.…”

Photoredox and Copper‐Catalyzed Sulfonylphosphorothiolation of Alkenes toward β‐Sulfonyl Phosphorothioates

“…Inspired by the well‐developed photocatalytic radical sulfonylations, sulfonyl chlorides appear to be the ideal sulfonyl surrogates as they are readily available, stable and biocompatible [11] . In addition, S ‐hydrogen phosphorothioates [P(O)SH] could be easily prepared from various (RO) 2 P(O)H and S 8 [12] . Therefore, this protocol would provide a straightforward strategy to obtain β‐sulfonyl phosphorothioates with diverse carbon frameworks (Scheme 1c).…”