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Metallophosphite-catalyzed Asymmetric Acylation of Alpha,beta-Unsaturated Amides

Metallophosphite-catalyzed Asymmetric Acylation of Alpha,beta-Unsaturated Amides

Mary R Nahm, Justin R Potnick, Peter S White, Jeffrey S Johnson

J Am Chem Soc. 2006 Mar 1;128(8):2751-6.

PMID: 16492064

Abstract:

The l-menthone-derived TADDOL phosphite 6b catalyzes highly enantioselective conjugate additions of acyl silanes to alpha,beta-unsaturated amides. p-Methoxybenzoyl cyclohexyldimethylsilane adds to a variety of N,N-dimethyl acrylamide derivatives in the presence of the lithium salt of 6b. In many instances the alpha-silyl-gamma-ketoamide product undergoes facile enantioenrichment (to 97-99% ee) upon recrystallization. Desilylation with HF.pyr affords the formal Stetter addition products. Baeyer-Villiger oxidation of the desilylated gamma-ketoamides affords useful ester products. An X-ray diffraction study of 6b reveals that the isopropyl group of the menthone ketal influences the position of the syn-pseudoaxial phenyl group in the TADDOL structure. Through a crossover experiment, the silicon migration step in the reaction mechanism is shown to be strictly intramolecular.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP29681569	Cyclohexyldimethylsilane		29681-56-9	Price

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