Details

Autor(en) / Beteiligte

• Yu, Kuan
• Yang, Zhen‐Ning
• Liu, Chun‐Hui
• Wu, Shao‐Qi
• Hong, Xin
• Zhao, Xiao‐Li
• Ding, Hanfeng

Titel

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

Ist Teil von

• Angewandte Chemie International Edition, 2019-06, Vol.58 (25), p.8556-8560

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2019

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A new TiIII‐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. Fusing cycles: A new TiIII‐mediated reductive epoxide‐opening/Beckwith–Dowd rearrangement efficiently assembles the bicyclo[3.2.1]octane framework of highly oxidized grayanane diterpenoids. This reaction, along with a CuII‐catalyzed intramolecular cyclopropanation, a diastereoselective oxidative dearomatization‐induced (ODI) Diels–Alder cycloaddition, and a MeReO3‐catalyzed Rubottom oxidation, were key steps in the first total syntheses of rhodomolleins XX and XXII.