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Intramolecular Dearomative Oxidative Coupling of Indoles: A Unified Strategy for the Total Synthesis of Indoline Alkaloids
Alternative Title吲哚的分子内去芳构化氧化偶联: 一个有用的吲哚类生物碱全合成策略
Zi WW(资伟伟); Zuo ZW(左智伟); Ma DW(马大为)
Source PublicationAccounts Chem. Res.
AbstractCONSPECTUS: Indole alkaloids, one of the largest classes of alkaloids, serve as an important and rich source of pharmaceuticals and have inspired synthetic chemists to develop novel chemical transformations and synthetic strategies. Many biologically active natural products contain challenging indoline scaffolds, which feature a C3 all-carbon quaternary stereocenter that is often surrounded by a complicated polycyclic ring system. The creation of this quaternary stereocenter creates an inherent synthetic challenge because the substituents on the carbon center cause high steric repulsion. In addition, the presence of nitrogen atoms within the surrounding polycyclic rings can lead to synthetic difficulties. Oxidative coupling between two sp(3)-hybridized carbon anions provides a unique and powerful method for building C-C single bonds, especially for generating a C-C bond that joins one or two vicinal quaternary stereocenters. Although chemists have known of this transformation for a long time, they have only applied this reaction in total synthesis of complex natural products during the past decade. The progress of this class of reaction depends on the use of indole moieties as coupling partners. In this Account, we summarize our recent efforts to develop iodine-mediated intramolecular dearomative oxidative coupling (IDOC) reactions of indoles as part of a unified strategy for the total synthesis of three classes of indoline alkaloids. We categorized these IDOC reactions into three types based on their mode of connection to the indole moiety. In type I, the carboanion nudeophile was tethered to the indole at the C3 position. This reaction enabled the assembly of skeleton A, which features a Spiro ring at the C3 position of the indole. We demonstrated the efficiency of this method by quickly assembling two classes of tetracyclic compounds and completing the total synthesis of (-)-communesins F, A, and B. For the type II IDOC reactions, the carboanion nudeophile residing at the C2 position of the indole formed a quaternary center at the C3 position of indole to produce skeleton B. We applied this IDOC reaction to synthesize two akuammiline alkaloids, vincorine and aspidophylline A. Type III IDOC reactions employed substrates with a preinstalled ring at the C2 and C3 positions of the indole. These transformations proceeded smoothly to afford polycyclic ring system C, which we used in the first enantioselective total synthesis of Kopsia alkaloid methyl N-decarbomethoxychanofruticosinate. These results further demonstrate how new chemical strategies and reactions facilitate both the first total syntheses of natural products and the discovery of more efficient synthetic routes.
Subject Area生命有机化学
Indexed BySCI
WOS IDWOS:000351326900022
Citation statistics
Cited Times:135[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Corresponding AuthorMa DW(马大为)
Affiliation中科院上海有机化学研究所, 生命有机化学国家重点实验室
Recommended Citation
GB/T 7714
Zi WW,Zuo ZW,Ma DW. Intramolecular Dearomative Oxidative Coupling of Indoles: A Unified Strategy for the Total Synthesis of Indoline Alkaloids[J]. Accounts Chem. Res.,2015,48(3):702-711.
APA 资伟伟,左智伟,&马大为.(2015).Intramolecular Dearomative Oxidative Coupling of Indoles: A Unified Strategy for the Total Synthesis of Indoline Alkaloids.Accounts Chem. Res.,48(3),702-711.
MLA 资伟伟,et al."Intramolecular Dearomative Oxidative Coupling of Indoles: A Unified Strategy for the Total Synthesis of Indoline Alkaloids".Accounts Chem. Res. 48.3(2015):702-711.
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