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Transition-Metal-Catalyzed Asymmetric Allylic Dearomatization Reactions
Alternative Title过渡金属催化的不对称烯丙基去芳构化反应
Zhuo CX(卓春祥); Zheng C(郑超); You SL(游书力)
2014
Source PublicationAccounts Chem. Res.
Volume47Issue:8Pages:2558-2573
AbstractCONSPECTUS: Dearomatization reactions serve as powerful methods for the synthesis of highly functionalized, three-dimensional structures starting with simple planar aromatic compounds. Among processes of this type, catalytic asymmetric dearomatization (CADA) reactions are attractive owing to the large number of aromatic compounds that are readily available and the fact that they enable direct access to enantiopure polycycles and spirocycles, which frequently are key structural motifs in biologically active natural products and pharmaceuticals. However, as a consequence of their high stabilities, arenes only difficultly participate in dearomatization reactions that take place with high levels of enantioselectivity. Transition-metal-catalyzed asymmetric allylic substitution reactions have been demonstrated to be powerful methods for enantioselective formation of C-C and C-X (X = O, N, S, etc.) bonds. However, the scope of these processes has been explored mainly using soft carbon nudeophiles, some hard carbon nucleophiles such as enolates and preformed organometallic reagents, and heteroatom nucleophiles. Readily accessible aromatic compounds have been only rarely used directly as nudeophiles in these reactions. In this Account, we present the results of studies we have conducted aimed at the development of transition-metal-catalyzed asymmetric allylic dearomatization reactions. By utilizing this general process, we have devised methods for direct dearomatization of indoles, pyrroles, phenols, naphthols, pyridines, and pyrazines, which produce various highly functionalized structural motifs bearing all-carbon quaternary stereogenic centers in a straightforward manner. In mechanistic investigations of the dearomatization process, we found that the five-membered spiroindolenines serve as intermediates, which readily undergo stereospecific allylic migration to form corresponding tetrahydro-1H-carbazoles upon treatment with a catalytic amount of TsOH. It is worth noting that no notable loss of the enantiomeric excess of the spiroindolenine derivatives takes place during the rearrangement process as a consequence of the intervention of a "three-center-two-electron"-type transition state, a proposal that has gained support from the results of DFT calculations. Equally intriguing, upon tuning of the electronic nature of the tethers, pyrroles or indoles undergo unprecedented Ir or Ru catalyzed intramolecular allylic alkylation promoted dearomatization/migration reactions. The operation of this novel reaction pathway provides additional information leading to a greater mechanistic understanding of the transition-metal-catalyzed enantioselective intramolecular functionalizations of pyrroles and indoles. The combined results of this effort provide not only methods for the efficient synthesis of highly enantioenriched fused and Spiro polycycles but also novel strategies in the field of asymmetric catalysis.
Subject Area金属有机化学
DOI10.1021/ar500167f
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Indexed BySCI
Language英语
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Document Type期刊论文
Identifierhttp://ir.sioc.ac.cn/handle/331003/39098
Collection金属有机化学国家重点实验室
Corresponding AuthorYou SL(游书力)
Affiliation中科院上海有机化学研究所
Recommended Citation
GB/T 7714
Zhuo CX,Zheng C,You SL. Transition-Metal-Catalyzed Asymmetric Allylic Dearomatization Reactions[J]. Accounts Chem. Res.,2014,47(8):2558-2573.
APA 卓春祥,郑超,&游书力.(2014).Transition-Metal-Catalyzed Asymmetric Allylic Dearomatization Reactions.Accounts Chem. Res.,47(8),2558-2573.
MLA 卓春祥,et al."Transition-Metal-Catalyzed Asymmetric Allylic Dearomatization Reactions".Accounts Chem. Res. 47.8(2014):2558-2573.
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