Oxaziridine-Mediated Oxidation Reaction of Thiolates To Give Sulfenates:  The First One-Pot Synthesis of Sulfoxides from Thiols

C=N Bond Activation and Hydration by an Iron(III) Complex with Asymmetric Sulfur Oxygenation

“…The slow conversion in air prompted us to employ other oxygenating agents for the preparation of the sulfur oxidation species. The S‐oxygenation derivatives [PPN][Fe(PyImS)(PyImSO 2 )] ( 2 , 60 % yield) and [PPN][Fe(PyImSO 2 ) 2 ] ( 3 , 55 % yield) were prepared by using 2 and 4 equivalents of an O‐atom‐transfer reagent, tert ‐butyl N ‐sulfonyloxaziridine (SOA), capable of oxygenating free thiols and Fe‐bound thiolate. [9e] The reactions in DMF were monitored and terminated (about 2 h) as judged by silica‐gel thin‐layer chromatography (TLC) (MeOH/EtOAc, 1:30): 1 , R f = 0.78; 2 , R f = 0.58; 3 , R f = 0.88.…”

Recent Advances in the Catalytic Asymmetric Reactions of Oxaziridines

“…Remarkably, oxaziridine 4 has served as an important family of organic active oxidizing agents due to its unique oxygen transfer capability. A series of nucleophiles that include sulfides [ 22 ], sulfoxides, alkenes [ 23 ], thiolates [ 24 ], phenols [ 25 , 26 ], naphthols, enolates, silyl enol ethers, selenides [ 27 ] and C-H bonds [ 28 , 29 , 30 , 31 ] could be oxidized via an asynchronous transition state in which N-O bond cleavage is faster than C-O bond cleavage ( Figure 2 ) [ 10 ]. Oxaziridinium salt 5 , first discovered by Lusinchi and co-workers in 1976 [ 32 , 33 ], was generated by the oxidation of the corresponding iminium salt with peracid or monoperoxysulfate.…”

7.28 Oxidation of Sulfur, Selenium, and Tellurium

“…238 Highly nucleophilic thiolate anions are smoothly oxidized by N-sulfonyl aziridines to give sulfenate anions able to undergo S N 2 displacement with an alkyl halide to afford aryl alkyl sulfoxides 34 in good yield. Electrochemical oxidation of sulfides is not a selective process since mixtures of sulfoxide and sulfone are usually observed.…”