Unified Strategy to Monoterpene lndole Alkaloids: Total Syntheses of (±)-Goniomitine, (±)-1,2-Dehydroaspidospermidine, (±)-Aspidospermidine, (±)-Vincadifformine, and (±)-Kopsihainanine A

被引：111
作者：
Wagnieres, Olivier [1 ]
Xu, Zhengren [1 ]
Wang, Qian [1 ]
Zhu, Jieping [1 ]
机构：
[1] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn, Lab Synth & Nat Prod, EPFL SB ISIC LSPN,BCH5304, CH-1015 Lausanne, Switzerland
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 42期
基金：
瑞士国家科学基金会;
关键词：
FORMAL TOTAL-SYNTHESIS; CATALYZED DECARBOXYLATIVE ALLYLATION; ENANTIOSELECTIVE TOTAL SYNTHESES; ASPIDOSPERMA QUEBRACHO-BLANCO; QUATERNARY CARBON CENTERS; INDOLE ALKALOIDS; NATURAL-PRODUCTS; MASS SPECTROMETRY; TRANSANNULAR CYCLIZATION; MEDIATED SYNTHESIS;
D O I：
10.1021/ja509329x
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Total syntheses of (+/-)-goniomitine, (+/-)-1,2-dehydroaspidospermidine, (+/-)-aspidospermidine, (+/-)-vincadifformine, and (+/-)-kopsihainanine A were achieved featuring two common key steps: (1) a palladium-catalyzed decarboxylative vinylation that provides quick access to cyclopentene intermediates containing all of the carbons present in the natural products and (2) an integrated oxidation/reduction/cyclization (iORC) sequence for skeletal reorganization that converts the cyclopentenes to the pentacyclic structures of the natural products. By incorporation of a geometric constraint to iORC substrates, both the chemoselectivity (C7 vs N1 cyclization) and the stereoselectivity (trans- vs cis-fused ring system) of the cyclization process can be controlled.
引用
收藏
页码：15102 / 15108
页数：7
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