Regio- and Stereoselective Hydrosulfonylation of Electron-Deficient Alkynes: Access to Both E- and Z-beta-Sulfonyl-alpha,beta-Unsaturated Carbonyl Compounds
Regio- and Stereoselective Hydrosulfonylation of Electron-Deficient Alkynes: Access to Both E- and Z-beta-Sulfonyl-alpha,beta-Unsaturated Carbonyl Compounds
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缺电子炔烃的区域选择性和立体选择性氢磺酰化：获得 E-和 Z-β-磺酰基-α,β-不饱和羰基化合物
DOI：
10.1002/adsc.201801032
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发表时间：
2018
影响因子：
5.4
通讯作者：
He Yan-Hong
中科院分区：
文献类型：
--
作者：
Zhang Wei;Johnson Gabriel M.;Guan Zhi;He Yan-Hong
开发了缺电子炔与亚磺酸钠或亚磺酸的无金属氢磺酰化反应，以获得E-和Z-β-磺酰基-α，β-不饱和羰基化合物。我们认为，该反应通过羟基丙二烯中间体提供了分子稳定的E异构体，或通过协调的三分子AdE 3机制提供了Z异构体。加成反应的立体选择性（synoranti）可以通过改变磺酰基来源和酸性缓冲溶液来控制。该方案具有广泛的底物范围内的内部或末端炔，包括各种取代的炔酮和炔基酯。该方法温和、高效、操作简单、易于放大。
A metal‐free hydrosulfonylation of electron‐deficient alkynes with sodium sulfinates or sulfinic acids to access bothE‐ andZ‐β‐sulfonyl‐α,β‐unsaturated carbonyl compounds has been developed. We propose that this reaction via a hydroxylallene intermediate delivers the thermodynamically stableEisomer, or via a concerted termolecular AdE3 mechanism affordsZisomer. The stereoselectivity of addition (synoranti) can be controlled by varying the sulfonyl sources and acidic buffer solutions. This protocol exhibits broad substrate scope for internal or terminal alkynes including various substituted ynones and alkynyl esters. This approach is mild, efficient, operationally simple and easy to be scaled‐up.