Allylic sulfoximines sulfinamides

In principle, allylic sulfoximines can be used as substrates for the allylation of an external nucleophile (Nu) if that nucleophile can compete with the sulfinamide anion C for the palladium(0) complex B or if the formation of D is reversible. In 1997 Pyne and co-workers99 reported that stabilized carbon and nitrogen nucleophiles can be efficiently allylated in a regioselective manner using allylic sulfoximines and palladium(O) catalysis (Eq. 5). 

As discussed above the kinetic stability of allylic sulfoximines prevents them from going downhill to the thermodynamically favored sulfinamides, which in turn is a precondition for their successful application as solutions for asymmetric d -synthons [ 13-15,20-32]. On the other hand, if it would be possible to make them rearrange to allylic amines with 1,3-chirality transfer, this would be an interesting entry to this class of compounds (Scheme 6). ... 

Pd(0)-catalyzed rearrangement of allylic sulfoximines to sulfinamides has been developed recently and appears to be an efficient route to chiral allylic amines (Scheme 22). This reaction is also known to occur thermaUyt but only for y-phenyl-substituted... 

In 1995 Pyne and Dong95 found that the ally lie sulfoximine 165 underwent a facile and completely regioselective and efficient rearrangement to the allylic sulfinamide 166 in the presence of tetrakis(triphenylphosphine)palladium(0) ((PPh3)4Pd) catalyst (5 mol%) at room temperature. Mild base hydrolysis of the reaction mixture (10% aqueous sodium hydroxide/methanol, 1 10, room temperature, 2 h) gave pure sulfonamide 167 after purification by column chromatography (silica gel) in 90% overall yield. 

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