Dehydrative Synthesis of Functionalized Skipped Dienes from Stabilized Phosphonium Ylides and Allylic Alcohols in Water
Dehydrative Synthesis of Functionalized Skipped Dienes from Stabilized Phosphonium Ylides and Allylic Alcohols in Water
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DOI：
10.1002/adsc.201801266
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发表时间：
2019-03-05
影响因子：
5.4
通讯作者：
Tang, Lin
中科院分区：
文献类型：
--
作者：
Ma, Xiantao;Yu, Jing;Tang, Lin
在[Pd（allyl）Cl]（2）/dppf催化剂存在下，稳定的膦叶立德与烯丙醇在水中进行温和的脱水烷基化反应。广泛的芳基、杂芳基、烷基和甚至烯丙基叔醇可以容易地与稳定的磷鎓叶立德反应，具有高的区域选择性，用于以中到高产率有效合成官能化的跳过的二烯。通过高分辨质谱和扩散有序谱核磁共振研究了水的作用，结果表明，水在π-烯丙基钯配合物的形成过程中可能起着重要的氢键作用.然而，本方法不适用于水敏性磷叶立德。
A mild and extra activator-free dehydrative alkylation of stabilized phosphonium ylides with allylic alcohols in water is developed in the presence of [Pd(allyl)Cl](2)/dppf catalyst. A wide range of aryl, heteroaryl, alkyl and even allylic tertiary alcohols can readily react with stabilized phosphonium ylides with high regioselectivity for the efficient synthesis of functionalized skipped dienes in moderate to high yields. The role of water was investigated by means of a high-resolution mass spectrum and diffusion-ordered spectroscopy nuclear magnetic resonance, and the results revealed that water might play a crucial role in the formation of the pi-allylpalladium complex via hydrogen bond. However, the present method is not suitable for water-sensitive phosphonium ylides.