The Enantioselective Tsuji Decarboxylative Allylic Alkylation

Key words

decarboxylative allylic alkylation - enol carbonates - palladium catalysis

Significance

Although introduced as early as 1980 by Tsuji (Tetrahedron Lett. 1980, 21, 3199) and Saegusa (J. Am. Chem. Soc. 1980, 102, 6381), the enantioselective version of a decarboxylative allylation had not been disclosed until more than two decades later by Behenna and Stoltz. Using a chiral phosphinooxazoline (Phox) ligand, the palladium(0)-catalyzed decarboxylative asymmetric allylic alkylation (Pd-DAAA) of simple allyl enol carbonates provided access to chiral cycloalkanones with quaternary stereocenters at the α-position.

Comment

Using Trost-type ligands, Tunge (Org. Lett. 2004, 6, 4113) and Trost (J. Am. Chem. Soc. 2005, 127, 2846) independently reported related decarboxylative allylations controlling the stereochemistry at the β- and α-position of the ketone, respectively. Since its discovery, the Tsuji decarboxylative allylic alkylation has been studied in-depth, and the scope of this transformation has been considerably extended.

Review

J. James, M. Jackson, P. J. Guiry Adv. Synth. Catal. 2019, 361, 3016–3049.

Publication History

Article published online:
20 September 2022