2-Alkylidenesulfol-3-enes by (regio- and) stereoselective cheletropic addition of SO2 to (di)vinylallenes.
2-Alkylidenesulfol-3-enes by (regio- and) stereoselective cheletropic addition of SO2 to (di)vinylallenes.
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通过 SO2 与（二）乙烯基丙二烯的（区域和）立体选择性螯合加成得到 2-亚烷基磺基-3-烯。
DOI：
10.1021/ol050240p
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发表时间：
2005
期刊：
影响因子：
5.2
通讯作者：
Á. D. De Lera
中科院分区：
文献类型：
--
作者：
José A. Souto;C. López;O. N. Faza;R. Álvarez;Á. D. De Lera
[反应：见正文] SO(2) 与二乙烯基丙二烯的螯合加成具有区域选择性，如果几何形状相反的乙烯基存在竞争，则发生在取代最多的乙烯基丙二烯和 E 单元上。非立体面分化是由于试剂从丙二烯的较少取代方向接近以及乙烯基丙二烯末端的伴随的旋转运动而产生的，以提供空间上更拥挤的2-亚烷基磺基-3-烯异构体。 DFT 计算证实了这些螯合加成的区域选择性和立体选择性。
[reaction: see text] The cheletropic addition of SO(2) to divinylallenes is regioselective, taking place at the most substituted vinylallene and at the E unit if vinyl groups of opposite geometry are competing. Diastereofacial differentiation results from the approach of the reagent from the less-substituted direction of the allene and from the concomitant disrotatory movement of the termini of the vinylallene to afford the sterically more congested 2-alkylidenesulfol-3-ene isomer. DFT computations confirm the regio- and the stereoselectivity of these cheletropic additions.