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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Total synthesis of (+)-crocacin C using hidden symmetry
Mathieu Candy1, Gérard Audran, Hugues Bienaymé
1Aix-Marseille Université, Institut des Sciences Moléculaires de Marseille, iSm2 CNRS UMR 6263-équipe STeRéO, Campus Saint-Jérôme, 13397 Marseille cedex 20, France.
Abstract:
A highly convergent and protecting-group-free synthesis of (+)-crocacin C, featuring an enzymatic enantioselective desymmetrization of a meso-diol, a base-induced ring opening of a THP ring, and a one-pot hydrostannylation/Stille coupling as the key steps, is reported. The natural product was obtained in 11 steps and 22.3% overall yield starting from readily available oxabicycle 1. Finally, a unique enantioselective step, an enzymatic desymmetrization, revealed four stereogenic centers and created one in C4 of the THP furnishing the dense building block 4 with high enantioselectivity (ee >98%).
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