The total synthesis of proteasome inhibitors TMC-95A and TMC-95B: Discovery of a new method to generate cis-propenyl amides

Abstract

Silatropic and ene-like bond reorganizations (see scheme, left) were the key steps in the first total synthesis of the title compounds, which only differ in stereochemistry at the remote C36 stereocenter. Other key steps include a Suzuki biaryl construction, a diastereofacial dihydroxylation reaction, and a macrolactamization.