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光化学产生的羟基邻醌二甲烷的对映选择性有机催化狄尔斯-阿尔德捕获反应

Enantioselective Organocatalytic Diels-Alder Trapping of Photochemically Generated Hydroxy-o-Quinodimethanes.

作者信息

Dell'Amico Luca, Vega-Peñaloza Alberto, Cuadros Sara, Melchiorre Paolo

机构信息

ICIQ-Institute of Chemical Research of Catalonia, Barcelona Institute of Science and Technology, Avenida Països Catalans 16, 43007, Tarragona, Spain.

ICREA-Catalan Institution for Research and Advanced Studies, Passeig Lluís Companys 23, 08010, Barcelona, Spain.

出版信息

Angew Chem Int Ed Engl. 2016 Mar 1;55(10):3313-7. doi: 10.1002/anie.201509472. Epub 2016 Jan 21.

Abstract

The photoenolization/Diels-Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light-triggered process has never before succumbed to efforts to develop an enantioselective catalytic approach. Herein, we demonstrate how asymmetric organocatalysis provides simple yet effective catalytic tools to intercept photochemically generated hydroxy-o-quinodimethanes with high stereoselectivity. We used a chiral organic catalyst, derived from natural cinchona alkaloids, to activate maleimides toward highly stereoselective Diels-Alder reactions. An unconventional mechanism of stereocontrol is operative, wherein the organocatalyst is actively involved in both the photochemical pathway, by leveraging the formation of the reactive photoenol, and the stereoselectivity-defining event.

摘要

光烯醇化/狄尔斯-阿尔德策略为合成具有重要价值的苯并稠合碳环产物提供了直接途径。这一具有历史意义的光触发过程此前从未成功实现对映选择性催化方法的开发。在此,我们展示了不对称有机催化如何提供简单而有效的催化工具,以高立体选择性拦截光化学产生的羟基邻醌二甲烷。我们使用了一种源自天然金鸡纳生物碱的手性有机催化剂,来活化马来酰亚胺以进行高立体选择性的狄尔斯-阿尔德反应。一种非常规的立体控制机制在起作用,其中有机催化剂通过利用反应性光烯醇的形成,积极参与光化学途径以及决定立体选择性的过程。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/332b/4797706/2533195daf5d/ANIE-55-3313-g001.jpg

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本文引用的文献

1
Enantioselective catalysis of photochemical reactions.
Angew Chem Int Ed Engl. 2015 Mar 23;54(13):3872-90. doi: 10.1002/anie.201411409. Epub 2015 Feb 27.
2
The evolving role of chemical synthesis in antibacterial drug discovery.
Angew Chem Int Ed Engl. 2014 Aug 18;53(34):8840-69. doi: 10.1002/anie.201310843. Epub 2014 Jul 2.
3
A dual-catalysis approach to enantioselective [2 + 2] photocycloadditions using visible light.
Science. 2014 Apr 25;344(6182):392-6. doi: 10.1126/science.1251511.
4
Enantioselective Lewis acid catalysis of intramolecular enone [2+2] photocycloaddition reactions.
Science. 2013 Nov 15;342(6160):840-3. doi: 10.1126/science.1244809.
5
Rapid UV light-triggered macromolecular click conjugations via the use of o-quinodimethanes.
Macromol Rapid Commun. 2011 Jun 1;32(11):807-12. doi: 10.1002/marc.201100159. Epub 2011 Apr 5.
6
Attractive noncovalent interactions in asymmetric catalysis: links between enzymes and small molecule catalysts.
Proc Natl Acad Sci U S A. 2010 Nov 30;107(48):20678-85. doi: 10.1073/pnas.1006402107. Epub 2010 Oct 18.
7
Catalytic enantioselective Diels--Alder reactions: methods, mechanistic fundamentals, pathways, and applications.
Angew Chem Int Ed Engl. 2002 May 17;41(10):1650-67. doi: 10.1002/1521-3773(20020517)41:10<1650::aid-anie1650>3.0.co;2-b.
8
Asymmetric catalysis with bifunctional cinchona alkaloid-based urea and thiourea organocatalysts.
Chem Commun (Camb). 2008 Jun 14(22):2499-510. doi: 10.1039/b719249e. Epub 2008 Feb 21.
10
Highly enantioselective Diels-Alder reaction of a photochemically generated o-quinodimethane with olefins.
Angew Chem Int Ed Engl. 2003 Aug 11;42(31):3693-6. doi: 10.1002/anie.200351567.

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