Total Syntheses of Rhodomolleins XX and XXII: A Reductive Epoxide-Opening/Beckwith-Dowd Approach

Kuan Yu; Zhen-Ning Yang; Chun-Hui Liu; Shao-Qi Wu; Xin Hong; Xiao-Li Zhao; Hanfeng Ding

doi:10.1002/anie.201903349

Total Syntheses of Rhodomolleins XX and XXII: A Reductive Epoxide-Opening/Beckwith-Dowd Approach

Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8556-8560. doi: 10.1002/anie.201903349. Epub 2019 May 9.

Authors

Kuan Yu¹, Zhen-Ning Yang¹, Chun-Hui Liu¹, Shao-Qi Wu¹, Xin Hong¹, Xiao-Li Zhao², Hanfeng Ding¹

Affiliations

¹ Department of Chemistry, Zhejiang University, Hangzhou, 310058, China.
² Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai, 200062, China.

PMID: 31046184
DOI: 10.1002/anie.201903349

Abstract

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 MeReO₃ -catalyzed Rubottom oxidation, this approach has enabled the first total syntheses of rhodomolleins XX and XXII in 23 and 22 steps, respectively.

Keywords: Diels-Alder; cyclopropanation; radical reactions; terpenoids; total synthesis.

Publication types

Research Support, Non-U.S. Gov't

Abstract

Publication types

Grants and funding