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Total synthesis of TMC-95A and -B via a new reaction leading to Z-enamides. Some preliminary findings as to SAR.

Journal of the American Chemical Society (2004-05-20)
Songnian Lin, Zhi-Qiang Yang, Benjamin H B Kwok, Michael Koldobskiy, Craig M Crews, Samuel J Danishefsky
RÉSUMÉ

A full account of the total syntheses of proteasome inhibitors TMC-95A and -B is provided. A key feature of the syntheses involved installation of a cis-propenylamide moiety by a thermal rearrangement of an alpha-silylallyl amide. The scope and mechanism of the enamide-forming reaction are discussed. Also provided are some preliminary results from SAR studies. It was found that simplified analogues can retain the full potency of proteasome inhibition.

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[1,1′-Bis(diphénylphosphino)ferrocène]dichloropalladium(II), complexe avec le dichlorométhane