Surface-mediated reactions. 5. Oxidation of sulfides, sulfoxides, and alkenes with tert-butyl hydroperoxide

Highly Stereoselective Nucleophilic Epoxidation of Simple Vinyl Sulfoxides

“…Two difficulties associated with this approach to sulfinyl oxiranes B (Scheme ) were apparent at the inception of this research. Alkenyl sulfoxides A , R 1 ≠ H, display a relatively low reactivity with nucleophiles, and the sulfinyl functionality is labile toward oxidation, either at the vinyl sulfoxide stage, A , to produce vinyl sulfones C , which would afford racemic epoxy sulfones D , or at the sulfinyl oxirane stage, B , leading to scalemic epoxy sulfones D . Considering these potential problems, the viability and, at best, the facial selectivity of the proposed epoxidation became a matter of concern.…”

Stereoselective Nucleophilic Epoxidation of Vinyl Sulfoxides: A Novel Route to Enantiopure Sulfinyl Oxiranes,1

“…The reactivity of simple E alkenyl sulfoxides 2 and 3 was then studied. Phenyl-substituted sulfoxide 2 was found to be totally unreactive under a number of experimental conditions . The well-known lack of reactivity of 2 with nucleophiles prompted us to study 3 , but unfortunately, our initial efforts led to almost exclusive formation of sulfone 9 .…”

A Concise Review on Synthesis of Sulfoxides and Sulfones with Special Reference to Oxidation of Sulfides

“…Peroxy compounds such as hydrogen peroxide, organic hydroperoxides, peracids and ozone are well known sources of active oxygen and have been used for the oxidation of sulfides to sulfoxides. Among organic hydroperoxides, urea-hydrogen peroxide (UHP) [77], tert-butyl hydroperoxide (TBHP) [78], 2hydroperoxyhexafluoro-2-propanol [79], flavin hydroperoxide [80] and α-azohydroperoxide [81] are well documented as oxidants for sulfoxidation. In 1928 Lewin reported the use of perbenzoic acid for sulfoxidation of sulfides at room temperature [82] while Sakuraba et al reported the use of peracetic acid for the same oxidation [83].…”