Organocatalytic Asymmetric Cascade Reactions of 7-Vinylindoles: Diastereo- and Enantioselective Synthesis of C7-Functionalized Indoles
Organocatalytic Asymmetric Cascade Reactions of 7-Vinylindoles: Diastereo- and Enantioselective Synthesis of C7-Functionalized Indoles
复制标题
7-乙烯基吲哚的有机催化不对称级联反应：C7-官能化吲哚的非对映和对映选择性合成
DOI：
10.1002/chem.201405245
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Tu Shu-Jiang
中科院分区：
文献类型：
--
作者：
Shi Feng;Zhang Hong-Hao;Sun Xiao-Xue;Liang Jing;Fan Tao;Tu Shu-Jiang
通过对底物的合理设计，首次建立了7-乙烯基吲哚的催化不对称级联反应。在手性磷酸衍生物存在下与靛红衍生的3-吲哚基甲醇的级联反应允许非对映选择性和对映选择性合成C7-官能化吲哚以及构建环戊并[B]吲哚和螺羟吲哚框架（均> 95：5 d.r.，94-> 99%ee）。该方法不仅解决了催化不对称合成C7-功能化吲哚的巨大挑战，而且为构建具有优异光学纯度的具有生物重要性的环戊二烯并[B]吲哚和螺羟吲哚支架提供了有效方法。对反应途径和活化模式的研究表明，该级联反应通过乙烯基迈克尔加成/Friedel-Crafts过程进行，其中两种反应物的双氢键活化起着至关重要的作用。
The first catalytic asymmetric cascade reaction of 7‐vinylindoles has been established by the rational design of such substrates. Cascade reactions with isatin‐derived 3‐indolylmethanols in the presence of a chiral phosphoric acid derivative allow the diastereo‐ and enantioselective synthesis of C7‐functionalized indoles as well as the construction of cyclopenta[b]indole and spirooxindole frameworks (all >95:5 d.r., 94–>99 %ee). This approach not only addresses the great challenge of the catalytic asymmetric synthesis of C7‐functionalized indoles, but also provides an efficient method for constructing biologically important cyclopenta[b]indole and spirooxindole scaffolds with excellent optical purity. Investigation of the reaction pathway and activation mode has suggested that this cascade reaction proceeds through a vinylogous Michael addition/Friedel–Crafts process, in which dual H‐bonding activation of the two reactants plays a crucial role.