Synthesis of the ACDE tetracyclic skeleton in ceforalide B

被引:0
作者
Cong, Xiao-Wei [1 ]
Peng, Yu [2 ]
机构
[1] Lanzhou Univ, Coll Chem & Chem Engn, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China
[2] Southwest Jiaotong Univ, Sch Chem, Chengdu 610031, Peoples R China
基金
中国国家自然科学基金;
关键词
Benzenoid cephalotanes; All-carbon quaternary center; Michael addition; Aldol condensation; Tetracyclic skeleton; ASYMMETRIC TOTAL-SYNTHESIS; MICHAEL REACTION; CONJUGATE ADDITION; TRICYCLIC CORE; CHIRAL AMINE; ALDEHYDES; NORDITERPENOIDS; CATALYSIS; ORGANOCATALYST; CONSTRUCTION;
D O I
10.1016/j.tet.2025.134618
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Ceforalide B is a representative molecule with a complex rigid skeleton composed of ABCDE pentacycle in the benzenoid cephalotane-type norditerpenoids family, which contains five contiguous stereogenic centers involving an all-carbon quaternary center. An advanced intermediate with the ACDE rings has been synthesized from 3,5-dimethylphenol. While the organocatalyzed diastereoselective intramolecular Michael addition and aldol condensation reaction successfully secure the rapid construction of the ACD tricyclic framework, the Yb (OTf)3-catalyzed stereoselective hydroxymethylation, 1,2-addition, followed by a PDC-mediated oxidative rearrangement reaction also play important roles in elaborating this tricyclic core. Additionally, the late-stage C1 epimerization and the construction of bridging lactone for E ring by a Mitsunobu reaction were further used to build the tetracyclic carbon skeleton.
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页数:10
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