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Tailored Synthesis of Skeletally Diverse Stemona Alkaloids through Chemoselective Dyotropic Rearrangements of β‐Lactones
Author(s) -
Guo Zhen,
Bao Ruiyang,
Li Yuanhe,
Li Yunshan,
Zhang Jingyang,
Tang Yefeng
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202102614
Subject(s) - chemistry , chemoselectivity , stereospecificity , tricyclic , stereochemistry , cycloaddition , combinatorial chemistry , substrate (aquarium) , alkyl , aryl , organic chemistry , catalysis , oceanography , geology
The collective synthesis of skeletally diverse Stemona alkaloids featuring tailored dyotropic rearrangements of β‐lactones as key elements is described. Specifically, three typical 5/7/5 tricyclic skeletons associated with stemoamide, tuberostemospiroline and parvistemonine were first accessed through chemoselective dyotropic rearrangements of β‐lactones involving alkyl, hydrogen, and aryl migration, respectively. By the rational manipulation of substrate structures and reaction conditions, these dyotropic rearrangements proceeded with excellent efficiency, good chemoselectivity and high stereospecificity. Furthermore, several polycyclic Stemona alkaloids, including saxorumamide, isosaxorumamide, stemonine and bisdehydroneostemoninine, were obtained from the aforementioned tricyclic skeletons through late‐stage derivatizations. A novel visible‐light photoredox‐catalyzed formal [3+2] cycloaddition was also developed, which offers a valuable tool for accessing oxaspirobutenolide and related scaffolds.