Oxidations of Thioketones by Singlet and Triplet Oxygen

Article abstract of DOI:10.1021/jo00340a027

Oxidation of di-tert-butyl thioketone (1) and 2,2,4,4-tetramethylcyclobutyl thioketone (2) by singlet oxygen yields the corresponding sulfine and ketone; in the case of 1 the sulfine is the major product, whereas in 2 it is the ketone. 1,2,3-Dioxathietane has been suggested as the precursor for the ketones, and the zwitterionic/diradical peroxide is believed to be a common primary intermediate for both sulfine and ketone.Steric influence is felt both during primary interaction between singlet oxygen and thioketone and during the partitioning of the peroxide intermediate.Steric interaction is suggested as the reason for variations in the product distribution between 1 and 2.Singlet oxygen is also generated through energy transfer from the triplet state of thioketones.These excited states also directly react with oxygen to yield ketone.