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

页码：15102 / 15108

页数：7

共 106 条

[1] [Anonymous], 1967, J CHEM SOC CHEM COMM
[2] BAN Y, 1965, TETRAHEDRON LETT, P2261
[3] Exploiting the palladium [0]-catalysed Ullmann cross-coupling reaction in natural products chemistry:: application to a total synthesis of the alkaloid (±)-aspidospermidine
Banwell, MG
Lupton, DW
[J]. ORGANIC & BIOMOLECULAR CHEMISTRY, 2005, 3 (02) : 213 - 215
[4] Exploiting multiple nucleophilic sites on pyrrole for the assembly of polyheterocyclic frameworks:: application to a formal total synthesis of (±)-aspidospermidine
Banwell, MG
Smith, JA
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 2002, (23): : 2613 - 2618
[5] Synthesis of (-)-Pseudotabersonine, (-)-Pseudovincadifformine, and (+)-Coronaridine Enabled by Photoredox Catalysis in Flow
Beatty, Joel W.
Stephenson, Corey R. J.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (29) : 10270 - 10273
[6] BIEMANN K, 1961, TETRAHEDRON LETT, P485, DOI 10.1016/S0040-4039(00)71759-X
[7] APPLICATION OF MASS SPECTROMETRY TO STRUCTURE PROBLEMS .10. ALKALOIDS OF BARK OF ASPIDOSPERMA QUEBRACHO BLANCO
BIEMANN, K
SPITELLER, G
SPITELLERFRIEDMANN, M
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (05) : 631 - &
[8] Amidation of esters assisted by Mg(OCH3)2 or CaCl2
Bundesmann, Mark W.
Coffey, Steven B.
Wright, Stephen W.
[J]. TETRAHEDRON LETTERS, 2010, 51 (30) : 3879 - 3882
[9] A Concise Total Synthesis of (±)-Trigonoliimine B
Buyck, Thomas
Wang, Qian
Zhu, Jieping
[J]. ORGANIC LETTERS, 2012, 14 (05) : 1338 - 1341
[10] WEITERE ALKALOIDE AUS DEN BLATTERN VON PLEIOCARPA TUBICINA - UMWANDLUNG VON (-)-QUEBRACHAMIN IN )+)-1,2-DEHYDROASPIDOSPERMIDIN
BYCROFT, BW
PATEL, MB
SCHMID, H
SCHUMANN, D
[J]. HELVETICA CHIMICA ACTA, 1964, 47 (05) : 1147 - &

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