Synthesis of the Strychnos Alkaloid (-)-Strychnopivotine and Confirmation of its Absolute Configuration

被引：13
|
作者：
Maertens, Gaetan [1 ]
Canesi, Sylvain [1 ]
机构：
[1] Univ Quebec, Lab Methodol & Synth Prod Nat, CP 8888,Succ Ctr Ville, Montreal, PQ H3C 3P8, Canada
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 21期
基金：
加拿大创新基金会; 加拿大自然科学与工程研究理事会;
关键词：
alkaloid; chiral auxiliary; desymmetrization; hypervalent iodine; total synthesis; WIELAND-GUMLICH ALDEHYDE; PINACOL TANDEM PROCESS; FORMAL TOTAL-SYNTHESIS; ENANTIOSELECTIVE TOTAL-SYNTHESIS; PALLADIUM-CATALYZED CYCLIZATION; HYPERVALENT IODINE REAGENT; CARBON BOND FORMATION; PHENOL DEAROMATIZATION; NUCLEOPHILIC-SUBSTITUTION; ASYMMETRIC-SYNTHESIS;
D O I：
10.1002/chem.201601319
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The first enantioselective synthesis of (-)-strychnopivotine from a known and inexpensive phenol has been achieved in 15 steps. The strategy is based on a new diastereoselective aza-Michael-enol-ether cascade desymmetrization of a dienone, guided by a removable lactic acid-derived chiral auxiliary. Synthesis involves a phenol dearomatization, a conjugated silicon addition, a stereoselective double reductive amination, and two Heck-type carbopalladations as key steps. The absolute configuration of the natural compound, which, to date, has been uncertain, was confirmed by using circular dichroism (CD) spectroscopy and X-ray analyses.
引用
收藏
页码：7090 / 7093
页数：4
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