Synfacts 2022; 18(10): 1117
DOI: 10.1055/s-0042-1752971
Metals in Synthesis

The Enantioselective Tsuji Decarboxylative Allylic Alkylation

Contributor(s):
Martin Oestreich
,
Hendrik F. T. Klare
,
Nektarios Kranidiotis-Hisatomi
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.
 

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.


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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.


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Review

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


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Publication History

Article published online:
20 September 2022

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