Total Synthesis of (± plus )-Maistemonine, (±)-Stemonamide, and (±)-Isomaistemonine

被引：56
作者：
Chen, Zhi-Hua
Chen, Zhi-Min
Zhang, Yong-Qiang
Tu, Yong-Qiang [1 ]
Zhang, Fu-Min
机构：
[1] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 76卷 / 24期
关键词：
INTRAMOLECULAR SCHMIDT REACTION; ASYMMETRIC TOTAL-SYNTHESIS; BETA-DICARBONYL COMPOUNDS; EFFICIENT TOTAL-SYNTHESIS; STEMONA-JAPONICA-MIQ; CONCISE SYNTHESIS; FORMAL SYNTHESIS; ALKALOIDS; ROOTS; REDUCTION;
D O I：
10.1021/jo202042x
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A full account of the total synthesis of (+/-)-maistemonine, (+/-)-stemonamide, and (+/-)-isomaistemonine is presented. Two approaches have been developed to construct the basic pyrrolo[1,2-a]azepine core of the Stemona alkaloids, featuring a tandem semipinacol/Schmidt rearrangement of a secondary azide and a highly stereoselectively desymmetrizing intramolecular Schmidt reaction, respectively. To build the common spiro-gamma-butyrolactone, a new protocol was carried out by utilizing an intramolecular ketone-ester condensation as the key transformation. The vicinal butyrolactone moiety of (+/-)-maistemonine was stereoselectively introduced via a one-pot procedure involving the epimerization at C-3 and carbonyl allylation/lactonization. Moreover, (+/-)-stemonamide was divergently synthesized from a common intermediate, and (+/-)-isomaistemonine was obtained via the epimerization of (+/-)-maistemonine at C-12.
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收藏
页码：10173 / 10186
页数：14
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