Categories: C-P Bond Formation >

Synthesis of phosphinates and phosphinic acid derivatives

Recent Literature

Deprotonation of various H-phosphinate esters with LHMDS at low temperature and subsequent alkylation takes place with a wide range of electrophiles. The approach can be employed to access some GABA analogues. The isolated yields are moderate to good.
I. Abrunhosa-Thomas, C. E. Sellers, J.-L. Montchamp, J. Org. Chem., 2007, 72, 2851-2856.

A convenient and efficient copper-catalyzed approach for P-arylation of organophosphorus compounds containing P-H uses the commercially available and inexpensive proline and pipecolinic acid as ligands. The method can provide an entry to arylphosphonates, arylphosphinates and arylphosphine oxides.
C. Huang, X. Tang, H. Fu, Y. Jiang, Y. Zhao, J. Org. Chem., 2006, 71, 5020-5022.

A stereospecific radical or base-catalyzed addition of the easily available (-)menthyl phenylphosphinate to alkenes gave various optically pure alkylphenylphosphinates.
L.-B. Han, C.-Q. Zhao, J. Org. Chem., 2005, 70, 10121-10123.

L.-B. Han, C.-Q. Zhao, J. Org. Chem., 2005, 70, 10121-10123.

Ethyl phosphinate adds to alkenes and alkynes under thermal radical conditions with AIBN as the initiator to give H-phosphinates in good yields.
M. I. Antczak, J.-L. Montchamp, Synthesis, 2006, 3080-3084.

M. I. Antczak, J.-L. Montchamp, Synthesis, 2006, 3080-3084.

Arylhydroxymethylphosphinic acid derivatives were prepared by a palladium(0) catalysed arylation of ethyl benzyl­oxymethylphosphinate with aryl halides followed by subsequent hydrogenolysis of the benzyl protecting group and hydrolysis of the ester function.
H.-J. Cristau, A. Hervé, F. Loiseau, D. Virieux, Synthesis, 2003, 2216-2220.

Various palladium catalysts promote the mild addition of hypophosphorous derivatives ROP(O)H₂ to alkenes and alkynes in good yields. With styrene and terminal alkynes, the regioselectivity (linear versus branched products) can be controlled to some extent with the catalytic system employed.
S. Deprele, J.-L. Montchamp, J. Am. Chem. Soc., 2002, 124, 9386-9387.

S. Deprele, J.-L. Montchamp, J. Am. Chem. Soc., 2002, 124, 9386-9387.

A novel palladium-catalyzed allylation of H₃PO₂ with allylic alcohols produces allylic-H-phosphinic acids and water, in the absence of additives. Primary H-phosphinic acids are obtained in excellent yields, whereas secondary H-phosphinic acids react sluggishly.
K. Bravo-Altamirano, J.-L. Montchamp, Org. Lett., 2006, 8, 4169-4171.