[reaction: see text] The combination of catalytic palladium(0) and Trost ligand provides an effective catalyst for the rearrangement of allyl beta-ketoesters. The mechanism of the transformation involves formation of pi-allyl palladium intermediates which undergo enantioselective attack by ketone enolates. Decarboxylation of beta-ketocarboxylates allows regiospecific generation of enolates under extremely mild conditions.

Protected homoallylic amines are synthesized by the decarboxylative coupling of alpha-amino acid derivatives. The catalytic C-C bond-forming reaction relies on the bioinspired decarboxylative metalation of alpha-amino acids to produce alpha-amino anion equivalents. The alpha-amino anion equivalents are intercepted by pi-allyl palladium electrophiles to produce substituted homoallylic amines.

[reaction: see text] Bipyridyl(pentamethylcyclopentadienyl)ruthenium chloride is an efficient catalyst for the formal [3,3] rearrangement of allyl beta-ketoesters. The mechanism of the transformation involves formation of pi-allyl ruthenium intermediates, which are selectively attacked at the more substituted allyl terminus by freely diffusing enolates. Decarboxylation of beta-ketocarboxylates allows generation of enolates under extremely mild conditions.

Keywords: Decarboxylation / Palladium enolates / Aldol / Allylic alkylation / Carroll rearrangement Transition metal catalyzed decarboxylation of β-keto acids and esters provides a convenient route for the regiospecific generation of enolates under neutral conditions. Enolates generated by decarboxylation have been utilized in aldol and Michael additions as well as allylic alkylations. The

The ruthenium-catalyzed stereospecific decarboxylative allylation of ketone enolates provides access to gamma,delta-unsaturated ketones with good yields and enantio-enrichments.