With
palladium(0) as a
catalyst, the reaction (Tsuji, 1980) is much milder (path
B) with an intermediate allyl cation / carboxylate
organometallic complex. Decarboxylation precedes allylation as evidenced by this reaction catalyzed by
tetrakis(triphenylphosphine)palladium(0): The first reported
asymmetric rearrangement is catalyzed by
tris(dibenzylideneacetone)dipalladium(0) and the
Trost ligand: A similar reaction uses additional
naphthol. This reaction delivers the main
enantiomer with 88%
enantiomeric excess. It remains to be seen if this reaction will have a wide scope because the
acetamido group appears to be a prerequisite. The same catalyst but a different ligand is employed in this
enantioconvergent reaction: The scope is extended to asymmetric α-alkylation of
ketones masked as their enol
carbonate esters: == References ==