Catalytic Asymmetric Arylation of 3-Indolylmethanols: Enantioselective Synthesis of 3,3 '-Bis(indolyl)oxindoles with High Atom Economy
Catalytic Asymmetric Arylation of 3-Indolylmethanols: Enantioselective Synthesis of 3,3 '-Bis(indolyl)oxindoles with High Atom Economy
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DOI：
10.1002/cctc.201500093
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发表时间：
2015
期刊：
影响因子：
4.5
通讯作者：
Shi Feng
中科院分区：
文献类型：
--
作者：
Sun Xiao-Xue;Du Bai-Xiang;Zhang Hong-Hao;Ji Lei;Shi Feng
以原子经济的方式建立了3-吲哚基甲醇的催化对映选择性芳基化反应，该反应将靛红衍生的3-吲哚基甲醇和3-甲基吲哚组装成具有生物重要性的具有四元立体中心的3，3 ′-双（吲哚基）羟吲哚，产率高，对映选择性好（约99%产率和91：9对映体比）.该反应也代表了3，3 ′-双吲哚基羟吲哚的催化对映选择性合成，适用于广泛的底物，产生了一系列具有结构多样性的手性3，3 ′-双吲哚基羟吲哚。对照实验表明，3-吲哚基甲醇的吲哚部分中的N-OH基团对于获得良好的对映选择性是重要的，而3-甲基吲哚的N-OH基团通过与催化剂的氢键相互作用在反应性中起着至关重要的作用。
The catalytic enantioselective arylation of 3‐indolylmethanols has been established in an atom‐economic fashion, which assembles isatin‐derived 3‐indolylmethanols and 3‐methylindoles into biologically important 3,3′‐bis(indolyl)oxindoles bearing a quaternary stereogenic center in high yields and good enantioselectivities (≈99 % yield and 91:9 enantiomeric ratio). This reaction also represents the catalytic enantioselective synthesis of 3,3′‐bis(indolyl)oxindoles, which is applicable to a wide range of substrates, yielding a series of chiral 3,3′‐bis‐ (indolyl)oxindoles with structural diversity. Control experiments demonstrated that the NH group in the indole moiety of 3‐indolylmethanol is important in obtaining good enantioselectivity, whereas the NH group of 3‐methylindole plays a crucial role in the reactivity via the hydrogen bonding interaction with the catalyst.