Sulphoxides amino-, rearrangement

Amino acids, sulphoxide, radiolysis of 909 a-Amino acids, reactions of 776, 777 a-Aminosulphones, synthesis of 176 Aminosulphonyl radicals 1093 Aminosulphoxides rearrangement of 740 synthesis of 336 Andersen synthesis 60 / -Anilinosulphoxides, synthesis of 334, 335 Anion radicals 1048-1050 ESR spectra of 1050-1054 formation of during electrolysis 963 during radiolysis 892-897, 899, 903 Annulation 778, 781, 801, 802 Antibiotics, synthesis of 310 Arenesulphenamides 740 Arenesulphenates 623 reactions of 282 rearrangement of 719 Arenesulphinates 824, 959 chiral 618... 

Thermal and mercury(ii)-catalysed [3,3]sigmatropic rearangement of allylic trichloroacetimidates and allylic pseudo-ureas" e.g. geraniol, linalool) are useful for the 1,3-transposition of hydroxy- and amino-groups the former is synthetically preferred. The [2,3]sigmatropic rearrangement of allylic sulphoxides has been used to effect an alkylative 1,3-carbonyl transposition of enones (e.g. carvone). ... 

A combination of [4 + 2] cycloaddition and [2,3]-sigmatropic rearrangement has been used with effect in the synthesis of hasubanan derivatives. Thus the 1-butadienyl phenyl sulphoxide (456) reacts with the enamine (457) to yield (458) as a mixture of diastereoisomeric sulphoxides. Heating (458) in the presence of a thiophilic species drives the equilibrium over to the sulphenate ([2,3]-sigmatropic shift) as the latter is converted into the amino-alcohol (459). This annelation sequence may also be used with electron-deficient dienophiles by employing 1-butadienyl phenyl sulphide (460). ... 

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