Sulfides allyl, imidation

Besides commonly used TsN=IPh, TsNs can also be employed as a nitrene source. Bach and Korber have recently reported an Fe(iii)-catalyzed imidation of allyl sulfides 200 with iV-/ //-butyloxycarbonyl azide (BocNs), followed by [2,3]-sigmatropic rearrangement (Scheme 21). " The azide reacts with FeCl2 to generate Fe(iv) nitrene complex 201, which then reacts with allyl sulfide 200, to give an intermediate sulfimide 203, presumably through Fe(iii) intermediate 202. 

Scheme 75 Highly enantioselective imidation of allylic sulfides with chiral ruthenium complex 311...

Catalytic Nitrene Transfer to Heteroatoms. The experimental procedure described above for the copper-catalyzed aziridination of olefins can be applied to the imidation of sulfides, where CuOTf in conjunction with PhI=NTs mediates the formation of siilfimides in good yields (eq 95). Spontaneous [2,3] sigma-tropic rearrangements occur in the case of allylic sulfides. Chiral bis(oxazoline)-CuOTf complexes catalyze both reactions with acceptable enantioselectivities (eq 96). Chloratnine-T is also a suitable but less efficient nitrene precursor. Selenides undergo the same catalytic asymmetric imidation to afford selenimides albeit with lower yields and enantioselectivities. ... 

The synthesis of allyl sulfonamides by imidation of allyl sulfides with chloramine-T (TsNClNa) and subsequent [2,3]-sigmatropic rearrangement has been reported (Scheme 43). ... 

More recently it was found that methyl sulfide-iV-chlorosuccin-imide in toluene at 0°C gives good yields of ketones by the oxidation of primary and secondary alcohols. However, allylic and dibenzylic alcohols give halides. The latter alcohols can be oxidized to ketones with a dimethyl sulfoxide-chlorine reagent. 

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