Total synthesis and stereochemical reassignment of mandelalide A.
The total synthesis of the tunicate metabolite mandelalide A and the correction of its originally assigned stereochemistry are reported. Key features of the convergent, fully stereocontrolled route include the use of a Prins cyclization for the diastereoselective construction of the tetrahydropyran subunit, Rychnovsky-Bartlett cyclization for the preparation of the tetrahydrofuran moiety, Suzuki coupling, Horner-Wadsworth-Emmons macrocyclization, and glycosylation to append the L-rhamnose-derived pyranoside.
Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Xili, Nanshan District, Shenzhen, 518055 (China).
Honghui
H
Lei
Jialei
J
Yan
Jie
J
Yu
Yuqing
Y
Liu
Zhuo
Z
Wang
Zhengshuang
Z
Xu
Tao
T
Ye
D003500:Cyclization; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism
D018942:Macrolides; C000589407:mandelalide A
configuration determination; diastereoselectivity; marine macrolides; structure elucidation; total synthesis