题名 | Construction of Axially Chiral Compounds via Asymmetric Organocatalysis |
作者 | |
通讯作者 | Tan, Bin |
发表日期 | 2018-02
|
DOI | |
发表期刊 | |
ISSN | 0001-4842
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EISSN | 1520-4898
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卷号 | 51期号:2页码:534-547 |
摘要 | Axially chiral compounds have received much attention from chemists because of their widespread appearance in natural products, biologically active compounds, and useful chiral ligands in asymmetric catalysis. Because of the importance of this structural motif, the catalytic enantioselective construction of axially chiral scaffolds has been intensively investigated, and great progress has been accomplished. However, the majority of methodologies in this field focus on the use of metal catalysis, whereas approaches involving organocatalysis have started to emerge only recently. This Account describes certain advances in the organocatalytic asymmetric synthesis of axially chiral compounds involving the following strategies: kinetic resolution, desymmetrization, cyclization/addition, direct arylation, and so on. We began our investigation by developing a highly efficient strategy for the kinetic resolution of axially chiral BINAM derivatives involving a chiral Bronsted acid-catalyzed imine formation and transfer hydrogenation cascade process, thereby providing a convenient route to generate chiral BINAM derivatives in high yields with excellent enantioselectivities. The desymmetrization of 1-aryltriazodiones (ATADs) through an organocatalyzed tyrosine clicklike reaction wherein a nucleophile was added to the ATAD afforded an interesting type of axially chiral N-arylurazole in an excellent remote enantiocontrolled manner. We then focused on a direct construction strategy involving cyclization and the addition strategy given the inherent limitations of the kinetic resolution in terms of the chemical yield and the desymmetrization in terms of the substrate scope. By utilizing the catalytic enantioselective Paal-Knorr reaction, we disclosed a general and efficient cyclization method to access enantiomerically pure arylpyrroles. The direct heterocycle formation and the stepwise method, which was executed in a one-pot fashion containing enantioselective cyclization and subsequent aromatization, were successfully applied for the construction of diverse axially chiral arylquinazolinones catalyzed by chiral Bronsted acids. We discovered the asymmetric organocatalytic approach to construct axially chiral styrenes through the 1,4-addition of arylalkynals in good chemical yields and enantioselectivities. Such structural motifs are important precursors for further transformations into biologically active compounds and useful synthetic intermediates and may have potential applications in asymmetric syntheses as olefin ligands or organocatalysts. To further tackle this challenge, we accomplished the phosphoric acid-catalyzed enantioselective direct arylative reactions of 2-naphthol and 2-naphthamine with quinone derivatives to deliver efficient access to a class of axially chiral BINOL and NOBIN derivatives in good yields with excellent enantioselectivities under mild reaction conditions. Most importantly, we discovered that the azo group can effectively perform as a directing and activating group for organocatalytic formal aryl C-H functionalization via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles were synthesized in good yields with excellent enantioselectivities. We anticipate that this strategy will foster the development of many other transformations and motivate a new enthusiasm for organocatalytic enantioselective aryl functionalization. Moreover, SPINOLs are fundamental synthetic precursors in the construction of other chiral organocatalysts and ligands. |
相关链接 | [来源记录] |
收录类别 | |
语种 | 英语
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重要成果 | ESI高被引
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学校署名 | 第一
; 通讯
|
资助项目 | Shenzhen Special Funds for the Development of Biomedicine, Internet, New Energy, and New Material Industries[JCYJ20170412151701379]
; Shenzhen Special Funds for the Development of Biomedicine, Internet, New Energy, and New Material Industries[KQJSCX20170328153203]
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WOS研究方向 | Chemistry
|
WOS类目 | Chemistry, Multidisciplinary
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WOS记录号 | WOS:000426014500035
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出版者 | |
ESI学科分类 | CHEMISTRY
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来源库 | Web of Science
|
引用统计 |
被引频次[WOS]:537
|
成果类型 | 期刊论文 |
条目标识符 | http://kc.sustech.edu.cn/handle/2SGJ60CL/28066 |
专题 | 理学院_化学系 |
作者单位 | South Univ Sci & Technol China, Dept Chem, Shenzhen 518055, Peoples R China |
第一作者单位 | 化学系 |
通讯作者单位 | 化学系 |
第一作者的第一单位 | 化学系 |
推荐引用方式 GB/T 7714 |
Wang, Yong-Bin,Tan, Bin. Construction of Axially Chiral Compounds via Asymmetric Organocatalysis[J]. ACCOUNTS OF CHEMICAL RESEARCH,2018,51(2):534-547.
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APA |
Wang, Yong-Bin,&Tan, Bin.(2018).Construction of Axially Chiral Compounds via Asymmetric Organocatalysis.ACCOUNTS OF CHEMICAL RESEARCH,51(2),534-547.
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MLA |
Wang, Yong-Bin,et al."Construction of Axially Chiral Compounds via Asymmetric Organocatalysis".ACCOUNTS OF CHEMICAL RESEARCH 51.2(2018):534-547.
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条目包含的文件 | ||||||
文件名称/大小 | 文献类型 | 版本类型 | 开放类型 | 使用许可 | 操作 | |
acs.accounts.7b00602(5018KB) | -- | -- | 限制开放 | -- |
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