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Pd(II)/Pd(IV) Catalyzes Stereochemical Control in Rearrangement.
A new Pd-catalyzed concerted mechanism enables precise stereocontrol for decarboxylative semi-pinacol rearrangements of beta-hydroxy carboxylic acids.
A new Pd(II)/Pd(IV) catalyzed concerted mechanism enables precise stereochemical control in the decarboxylative semi-pinacol rearrangement of β-hydroxy carboxylic acids.
- The reaction proceeds via a six-membered Pd(IV) chelate that fragments with β-to-α migration while retaining absolute configuration of the migrating group and inverting the α-stereocenter.
- It achieves markedly higher migrating-group selectivity than classical Tiffeneau–Demjanov or Büchner–Curtius–Schlotterbeck reactions for unsymmetrical ketones.
- The approach is broadly applicable to both cyclic and acyclic ketones and aldehydes, eliminating the need for volatile diazo reagents in total synthesis workflows.