Molecular Catalyst Research Center, Chubu University, Kasugai, Aichi 487-8501 (Japan) http://www3.chubu.ac.jp/catalyst/.
Angew Chem Int Ed Engl. 2014 Dec 22;53(52):14472-5. doi: 10.1002/anie.201408893. Epub 2014 Oct 27.
α-Hydroxy phosphonic acids and their derivatives are highly bioactive structural motifs. It is now reported that these compounds can be accessed through the copper-catalyzed direct α-oxidation of β-ketophosphonates using in situ generated nitrosocarbonyl compounds as an electrophilic oxygen source. These reactions proceeded in high yields (up to 95 %) and enantioselectivities (up to >99 % ee) for both cyclic as well as acyclic substrates. This method was also applied for the synthesis of α,β-dihydroxy phosphonates and β-amino-α-hydroxy phosphonates.
α-羟基膦酸及其衍生物是高度生物活性的结构基序。据报道，这些化合物可以通过铜催化的原位生成的亚硝酰碳化合物作为亲电氧源的β-酮膦酸酯的直接α-氧化来获得。这些反应对于环状和非环状底物都具有高产率（高达 95%）和对映选择性（高达>99%ee）。该方法还可用于合成α，β-二羟基膦酸酯和β-氨基-α-羟基膦酸酯。
