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

S Lin, ZQ Yang, BHB Kwok, M Koldobskiy…

Index: Lin, Songnian; Yang, Zhi-Qiang; Kwok, Benjamin H. B.; Koldobskiy, Michael; Crews, Craig M.; Danishefsky, Samuel J. Journal of the American Chemical Society, 2004 , vol. 126, # 20 p. 6347 - 6355

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Citation Number: 112

Abstract

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 α-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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