Huang Hai, Denne Johanna, Yang Chou-Hsun, Wang Haobin, Kang Jun Yong
Department of Chemistry and Biochemistry, University of Nevada Las Vegas, 4505 South Maryland Parkway, Las Vegas, NV, 89154-4003, USA.
Department of Chemistry, University of Colorado Denver, Denver, CO, 80217-3364, USA.
Angew Chem Int Ed Engl. 2018 May 28;57(22):6624-6628. doi: 10.1002/anie.201802082. Epub 2018 May 7.
A strategy for the direct functionalization strategy of inertial dialkyl phosphonates with hydroxy compounds to afford diverse mixed phosphonates with good yields and functional-group tolerance has been developed. Mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive P species (phosphoryl pyridin-1-ium salt), a key intermediate for this new synthetic transformation, is generated in situ from dialkyl phosphonate in the presence of Tf O/pyridine.
已开发出一种将惯性二烷基膦酸酯与羟基化合物直接官能团化的策略，以高产率和官能团耐受性得到多种混合膦酸酯。涉及核磁共振研究和密度泛函理论研究的机理研究表明，在三氟甲磺酸酯/吡啶存在下，由二烷基膦酸酯原位生成了一种前所未有的高活性磷物种（磷酰基吡啶-1-鎓盐），这是这种新合成转化的关键中间体。
