SIOC OpenIR  > 金属有机化学国家重点实验室
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)
Source PublicationAccounts Chem. Res.
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
Indexed BySCI
Citation statistics
Document Type期刊论文
Corresponding AuthorYou SL(游书力)
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.
Files in This Item:
File Name/Size DocType Version Access License
2014406.pdf(4338KB)期刊论文作者接受稿开放获取CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[卓春祥]'s Articles
[郑超]'s Articles
[游书力]'s Articles
Baidu academic
Similar articles in Baidu academic
[卓春祥]'s Articles
[郑超]'s Articles
[游书力]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[卓春祥]'s Articles
[郑超]'s Articles
[游书力]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.