Tsuji-Trost reaction neutral allylation

Thanks to the fundamental studies of Tsuji, Trost, and others, palladium-catalyzed allylic substitution has become a versatile, widely used process in organic synthesis [40]. The search for efficient enantioselective catalysts for this class of reactions is an important goal of current research in this field [41]. It has been shown that chiral phosphine ligands can induce substantial enantiomeric excesses in Pd-catalyzed reactions of racemic or achiral allylic substrates with nucleophiles [42]. Recently, promising results have also been obtained with chiral bidentate nitrogen ligands [43]. We have found that palladium complexes of neutral aza-semicorrin or methylene-bis(oxazoline) ligands are effective catalysts for the enantioselective allylic alkylation of l,3-diphenyl-2-propenyl acetate or related substrates with dimethyl malonate (Schemes 18 [25,30] and 19 [44]). 

The research groups of Trost and Tsuji have shown that in the presence of a palladium(O) catalyst vinyl epoxides can be regio- and stereo-selectively alkylated with various carbon acids under neutral conditions the main products are E-allylic alcohols resulting from 1,4-addition, e.g. (107) - (108). The reaction tolerates ester and ether groups. In the presence of a base, alkyl-lithiums... 

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