Behenna DC,
Stoltz BM.
*
California Institute of Technology, Pasadena, USA
The Enantioselective Tsuji Allylation.
J. Am. Chem. Soc. 2004;
126: 15044-15045
DOI:
10.1021/ja044812x
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.
