HETEROCYCLES [SOPhy]

Abstract :

Natural, non-natural and ent-14β-hydroxyandrostane derivatives closely related to the cardenolide and bufadienolide skeletons were readily available through highly diastereo-/enantioselective Diels–Alder reactions calling for high pressure or Lewis acid activation. Moreover, in the presence of (R)- or (S)-carvone as chiral dienophile, the Diels–Alder reaction took place under chemodivergent parallel kinetic resolution control. Based on experimental and DFT studies, reasonable mechanism insights were postulated to explain the concave/convex and endo/exo selectivities observed for the formation of the different Diels–Alder and Diels–Alder–Michael adducts.

Reference :

Clovis Peter, Philippe Geoffroy, Takatsugu Murata, Takayuki Tonoi, Isamu Shiina, and Michel Miesch

Diastereo–/Enantioselective Diels–Alder Synthesis of 14β-Hydroxysteroid Scaffolds: A Combined Experimental and DFT Study

HETEROCYCLES, Published online: 27th February, 2019 - DOI: 10.3987/COM-18-S(F)99

 

Contact chercheur :

Philippe Geoffroy, équipe SOPhy, Institut de Chimie (UMR 7177).