Synthesis of Sterically Encumbered Thiourea S-Oxides through Direct Thiourea Oxidation.

ABSTRACT: Thiourea S-oxides can be viewed as formal analogs of the currently unknown diamino-substituted Criegee intermediates (urea O-oxides). However, the preparation of such S-oxides is rather challenging, and the direct oxidation of thioureas typically only leads to formation of desulfurized products. Employing the accurate revDSD-PBEP86-D4 double hybrid density functional, it was found that the peracid mediated oxidation of thiourea S-oxides exhibits a lower reaction barrier than the oxidation of the corresponding thiourea itself in contrast to most other ordinary thioketones. The undesired overoxidation reactivity, which is associated with strong π-donation from the thiourea's nitrogen atoms, can be partially suppressed by introduction of bulky substituents and the utilization of protic solven

SUBMITTER: Medvedko S 

PROVIDER: S-EPMC10107457 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature