Semi-Synthesis of (+)-Digitoxigenin from Androstenedione.

The key steps of our synthesis were a Saegusa-Ito oxidation reaction, a direct C14 -hydroxylation, and a Stille cross-coupling. Keywords: cardiotonic steroids; digitoxigenin; androstenedione; Stille cross-coupling; hydroxylation; semi-synthesis EN cardiotonic steroids digitoxigenin androstenedione Stille cross-coupling hydroxylation semi-synthesis 2034 2036 3 10/09/23 20231024 NES 231024 Graph Cardenolides represent a unique family of natural products exhibiting positive inotropic activities. Reviewing the extensive literature, we found that no direct C14 -hydroxylation had been achieved; C14 hydroxylation has mainly been achieved through a Mukaiyama hydration reaction, which requires the construction of a C14-C15 unsaturated bond, resulting in multiple synthesis steps. Cardiotonic steroids, digitoxigenin, androstenedione, hydroxylation, semi-synthesis, Stille cross-coupling. [Extracted from the article]