Divergent Synthesis of Solanidine and 22-epi-Solanidine

被引:9
作者
Hou, Ling-Li [2 ]
Shi, Yong [1 ]
Zhang, Zhi-Dan [1 ]
Wu, Jing-Jing [1 ]
Yang, Qing-Xiong [2 ]
Tian, Wei-Sheng [1 ]
机构
[1] Chinese Acad Sci, Shanghai Inst Organ Chem, CAS Key Lab Synthet Chem Nat Subst, 345 Lingling Rd, Shanghai 200032, Peoples R China
[2] Guizhou Normal Univ, School Chem & Mat Sci, 116 Baoshan North Rd, Guiyang 550001, Guizhou, Peoples R China
基金
中国国家自然科学基金;
关键词
HIGHLY ENANTIOSELECTIVE SYNTHESIS; ALPHA-SOLANINE; SOLASODINE; GLYCOALKALOIDS; PROPARGYLAMINES; CYCLOPAMINE; METABOLITES; DEMISSIDINE; ANTICANCER; AZIDES;
D O I
10.1021/acs.joc.7b01133
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A divergent synthesis of solanidine and 22-epi-solanidine, two 25S natural steroidal alkaloids, from 25R-configured diosgenin acetate, is described. Initially, solanidine was synthesized through a series of transformations including a cascade ring-switching process of furostan-26-acid, an epimerization of C25 controlled by the conformation of six-membered lactone ring, an intramolecular Schmidt reaction, and an imine reduction/intramolecular aminolysis process. To address the epimerization issue during Schmidt reaction, an improved synthesis was developed, which also led to a synthesis of 22-epi-solanidine. In this synthesis, selective transformation of azido lactone to azido diol and amino diol was realized through a reduction relay tactic. The azido diol was transformed to solanidine via an intramolecular Schmidt reaction/N-alkylation/reduction process and to 22-epi-solanidirie via an intramolecular double N-alkylation process.
引用
收藏
页码:7463 / 7469
页数:7
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