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Total Syntheses of Rhodomolleins XX and XXII: A Reductive Epoxide‐Opening/Beckwith–Dowd Approach
Author(s) -
Yu Kuan,
Yang ZhenNing,
Liu ChunHui,
Wu ShaoQi,
Hong Xin,
Zhao XiaoLi,
Ding Hanfeng
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201903349
Subject(s) - epoxide , intramolecular force , cyclopropanation , chemistry , cycloaddition , bicyclic molecule , octane , medicinal chemistry , stereochemistry , catalysis , organic chemistry
A new Ti III ‐mediated reductive epoxide‐opening/ Beckwith–Dowd rearrangement process efficiently assembles the bicyclo[3.2.1]octane framework of highly oxidized grayanane diterpenoids. By incorporation of a Cu(tbs) 2 ‐catalyzed (tbs= N ‐ tert ‐butylsalicylaldiminato) intramolecular cyclopropanation, a diastereoselective oxidative dearomatization‐induced Diels–Alder cycloaddition and a MeReO 3 ‐catalyzed Rubottom oxidation, this approach has enabled the first total syntheses of rhodomolleins XX and XXII in 23 and 22 steps, respectively.