Total Syntheses of Rhodomolleins XX and XXII: A Reductive Epoxide‐Opening/Beckwith–Dowd Approach
作者:Kuan Yu、Zhen‐Ning Yang、Chun‐Hui Liu、Shao‐Qi Wu、Xin Hong、Xiao‐Li Zhao、Hanfeng Ding
DOI:10.1002/anie.201903349
日期:2019.6.17
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
一种新的Ti III介导的还原性环氧开放/ Beckwith-Dowd重排过程可有效地组装高度氧化的灰烷二萜类化合物的双环[3.2.1]辛烷骨架。由铜(TBS)的掺入2 -催化的(TBS = ñ -叔-butylsalicylaldiminato)分子内环丙烷,非对映选择性氧化脱芳构化诱导的第尔斯-阿尔德环加成和MeReO 3催化的鲁伯特姆氧化反应,这种方法已使所述第一全合成分别以23和22的步数测定XX和XXII的杜鹃花胶。