Oxidation of H-phosphonates with iodine by intramolecular support of a 2-pyridyl thermolabile protecting group.
Acceleration of H-phosphonate diester oxidation with iodine accompanied by a thermolabile protecting group (TPG) is presented. It is shown that the intermediate product of this reaction is an oxazaphospholidine oxide which forms a phosphate diester only when a 2-pyridyl TPG is applied. The intermediate product is formed with exocyclic nitrogen. The absolute configurations of phosphorothioate diesters, H-phosphonate diesters, and oxazaphospholidine oxides were determined. (31)P NMR spectroscopy was used to evaluate the relationship between chemical shift and absolute configuration at the phosphorus center of H-phosphonate diesters and oxazaphospholidine oxides.
Institute of Bioorganic Chemistry, Polish Academy of Sciences, Noskowskiego 12/14, 61-704 Poznań, Poland.
Tomasz
T
Ratajczak
Marcin K
MK
Chmielewski
D001372:Aza Compounds / Q000737:chemistry*; D004952:Esters; D007455:Iodine / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D063065:Organophosphonates / Q000737:chemistry*; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism
D001372:Aza Compounds; D004952:Esters; D063065:Organophosphonates; D011725:Pyridines; D007455:Iodine