The asymmetric hydrogenation of 2-phenethylacrylic acid as the key step for the enantioselective synthesis of Citralis Nitrile®

doi:10.1016/j.tetlet.2006.10.129

Tetrahedron Letters

Volume 47, Issue 52, 25 December 2006, Pages 9261-9265

https://doi.org/10.1016/j.tetlet.2006.10.129 Get rights and content

Abstract

A catalytic approach to the enantioselective synthesis of Citralis Nitrile^® (3-methyl-5-phenyl-pentanenitrile, a citrus-type odorant) is described. The key step is the transition-metal catalyzed asymmetric hydrogenation of 2-phenethylacrylic acid. Among the different catalysts tested, the most efficient appears to be the one formed by combining in situ [Ru(benzene)Cl₂]₂ with the atropisomeric diphosphine MeOBIPHEP and triethylamine, which allows us to obtain enantiomeric excesses up to 98% under mild conditions. Very good results (ees >80%) have also been obtained using iridium cationic complexes in combination with a phosphinooxazoline ligand.

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Acknowledgements

We are indebted to the reviewers for helpful comments and suggestions. Rhodia UK Ltd—Phosphorus Specialties and Derivatives is acknowledged for generously supplying the BINAP ligand. The work has been performed with the Financial Support of the MIUR (Cofin 2004).

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The asymmetric hydrogenation of 2-phenethylacrylic acid as the key step for the enantioselective synthesis of Citralis Nitrile®

Abstract

Graphical abstract

Section snippets

Acknowledgements

Appl. Catal. A: Gen.

Tetrahedron: Asymmetry

J. Mol. Catal. A: Chem.

J. Organomet. Chem.

Tetrahedron Lett.

J. Mol. Catal. A: Chem.

Tetrahedron Lett.

Tetrahedron: Asymmetry

J. Organomet. Chem.

Helv. Chim. Acta

Org. Lett.

J. Am. Chem. Soc.

J. Org. Chem.

J. Org. Chem.

The asymmetric hydrogenation of 2-phenethylacrylic acid as the key step for the enantioselective synthesis of Citralis Nitrile^®