P-O Bond Formation
Phosphorylation of amines, alcohols, and sulfoximines provides various phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates using molecular iodine as a catalyst and H2O2 as the sole oxidant under mild reaction conditions.
J. Dhineshkumar, K. R. Prabhu, Org. Lett., 2013, 15, 6062-6065.
Reaction of phosphorus oxychloride with a primary alcohol and triethylamine in toluene, followed by filtration and treatment with steam, gives dialkyl phosphates in good yield and essentially free from trialkyl phosphate impurities.
R. A. Aitken, C. J. Colett, S. T. E. Mesher, Synthesis, 2012, 44, 2515-2518.
An efficient electrophilic fluorination of secondary phosphine oxides with Selectfluor provides direct access to phosphoric fluorides in good yield under mild conditions. In addition, one-pot P-O bond construction is achieved in the presence of water or alcohols to provide phosphinic acids or phosphinates.
Q. Chen, J. Zeng, X. Yan, Y. Huang, C. Wen, X. Liu, K. Zhang, J. Org. Chem., 2016, 81, 10043-10048.
Copper catalysis allows the direct oxygen-arylation of dialkyl phosphonates with diaryliodonium salts. This reaction proceeds with a wide range of phosphonates and phosphoramidates under mild conditions and gives mixed alkyl aryl phosphonates in very good yields and very good selectivity.
M. Fañanás-Mastral, B. L. Feringa, J. Am. Chem. Soc., 2014, 136, 9894-9897.