Synfacts 2018; 14(10): 1041
DOI: 10.1055/s-0037-1610950
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Decarboxylative Allylic Alkylation of Acyclic Enol Carbonates

Mark Lautens
Liher Prieto
Alexy EJ, Zhang H. * Stoltz BM. * California Institute of Technology, Pasadena and Genentech Inc., South San Francisco, USA
Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates.

J. Am. Chem. Soc. 2018;
140: 10109-10112
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17. September 2018 (online)



The authors present the first enantio­selective palladium-catalyzed decarboxylative allylic alkylation of fully substituted non-cyclic enol carbonates. The reaction delivers the linear α-quaternary ketones in excellent yields. The phosphinooxazolidine ligand controls the stereoselectivity of the reaction regardless of the Z/E geometry of the enolate starting material.



This work outlines a general method to access linear α-quaternary ketones with high ­enantioselectivity. A dynamic kinetic resolution of the two Z/E geometries of the enolate starting material is postulated under optimal reaction conditions, which comprise the use of an electron-deficient phosphinooxazolidine ligand.