格林，由次磷酸和苄醇通过钯催化合成苄基次膦酸酯
Green, Palladium-Catalyzed Synthesis of Benzylic H-phosphinates from Hypophosphorous Acid and Benzylic Alcohols.
作者信息
Coudray Laëtitia, Montchamp Jean-Luc
机构信息
Department of Chemistry, Texas Christian University, Box 298860, Fort Worth, Texas 76129, USA, Fax: :(+1)-817-257-5851.
出版信息
European J Org Chem. 2008 Aug 1;2008(24):4101-4103. doi: 10.1002/ejoc.200800581.
Abstract
Benzylic alcohols cross-couple directly with concentrated H(3)PO(2) using Pd/xantphos (1 or 2 mol-%). Depending on the substrate, DMF at 110°C, or t-AmOH at reflux with a Dean-Stark trap, can be used. A broad range of benzylic alcohols reacted successfully in moderate to good yields. The preparation of other organophosphorus compounds (phosphinic and phosphonic acids) is also demonstrated.Asymmetric reaction with (R)-1-(2-naphthyl)ethanol provided the corresponding H-phosphinic acid in 77% ee. The methodology provides a green, PCl(3)-free, entry into benzylic-H-phosphinic acids.
摘要
苄醇可使用钯/联二萘二膦（1或2 mol%）与浓H₃PO₂直接进行交叉偶联反应。根据底物的不同，可以使用110°C的N,N-二甲基甲酰胺或带分水器回流的叔戊醇。多种苄醇都能成功反应，产率适中至良好。还展示了其他有机磷化合物（次膦酸和膦酸）的制备方法。与(R)-1-(2-萘基)乙醇的不对称反应以77%的对映体过量提供了相应的次膦酸。该方法提供了一种绿色、无PCl₃的制备苄基次膦酸的途径。
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