Synthesis of Phosphane Oxides and Phosphonates by Cerium-Mediated Addition of Organolithium Compounds to Chloro-Phosphorus Compounds

Abstract

The addition of organocerium reagents 2a-g to phosphinoyl benzyl group bound to the carbonyl moiety should be metallated. The latter reaction is the first reported synthesis chloride 1a or chlorophosphates 1b leads to the synthesis of phosphane oxides 3aa-ag and phosphonates 3bb, be in good of β-oxophosphane oxides by a simple reaction between enolates and a phosphorus(V) halide. to high yield. The reaction can be extended to cerium enolates 4 (of ketones) and 6 (of nitriles) except when aThe most common methods to prepare them [2c,6,7] are two-

Proline/Pipecolinic Acid-Promoted Copper-Catalyzed P-Arylation

“…This progress relied on the utilization of some special bidentate additives, for example, aliphatic diamines, 1,10-phenanthroline and its derivatives,2f ethylene glycol,5a diethylsalicylamide,5b amino acids, oxime-type and Schiff base ligands, thiophene-2-carboxylate, bidentate phosphines, diphosphinidenecyclobutene, and diphenyl pyrrolidine-2-phosphonate for N -arylation of amines/amides and 1-naphthoic acid,2a 2,2,6,6-tetramethylheptane-3,5-dione,2b phosphazene P 4 - t -Bu base,2c N,N -dimethylglycine,2d 8-hydroxyquinoline,2e and salicylal-doxime (Salox) 2g for O -arylation of substituted phenol or alcohol. Although arylphosphonates and phosphane oxides are of practical application, to the best of our knowledge, examples of copper-mediated C−P bond formation are rare 6i, here we report it and its analogue pipecolinic acid as efficient bidentate ligands for the formation of copper-catalyzed C−P bonds.…”