Categories: C-P Bond Formation >
Synthesis of phosphinates and phosphinic acid derivatives
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 novel and highly efficient Pd-catalyzed cross-coupling of triarylbismuths with various P(O)-H compounds proceeds smoothly without exclusion of moisture or air and provides valuable arylphosphonates, arylphosphinates, and arylphosphine oxides, with high atom-economy, operational simplicity of the procedure, and good to high yield.
T. Wang, S. Sang, L. Liu, H. Qiao, Y. Gao, Y. Zhao, J. Org. Chem., 2014, 79, 608-617.
An efficient use of arynes for C-P bond construction enables a mild process for the synthesis of aryl-phosphonates, -phosphinates, and -phosphine oxides. The reaction circumvents the relatively harsh reaction conditions using transition-metal-catalyzed P-arylation (Arbuzov/Hirao reaction).
R. A. Dhokale, S. B. Mhaske, Org. Lett., 2013, 15, 2218-2221.
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.
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.
A microwave-assisted hydrophosphinylation of unactivated alkenes with phosphinic acid and its derivatives under metal- and initiator-free conditions is operationally simple and seems to proceed via a radical mechanism. Good isolated yields were obtained using a reasonable excess of the appropriate reagent.
P. Troupa, G. Katsiouleri, S. Vassiliou, Synlett, 2015, 26, 2714-2719.
A palladium-catalyzed hydrophosphorylation of alkynes with P(O)-H compounds (i.e., H-phosphonates, H-phosphinates, secondary phosphine oxides, and hypophosphinic acid) provides Markovnikov adducts in high yields with high regioselectivity for both aromatic and aliphatic alkynes. The reaction tolerates a wide variety of functional groups.
T. Chen, C.-Q. Zhao, L.-B. Han, J. Am. Chem. Soc., 2018, 140, 3139-3155.
Efficient Cs2CO3-promoted phosphorylations or phosphinylations of various 1,1-dibromo-1-alkenes with readily available trialkyl phosphites, ethyl diphenylphosphinite, or diethyl phenylphosphonite under metal-free conditions provide valuable alkynylphosphonates, -phosphinates, and -phosphine oxides in very good yields.
Y. Wang, J. Gan, L. Liu, H. Yuan, Y. Gao, Y. Liu, Y. Zhao, J. Org. Chem., 2014, 79, 3678-3683.
A new, efficient method based on a palladium(0)-catalyzed reaction of propargylic derivatives with various phosphorus nucleophiles produces allenylphosphonates and their analogues with defined stereochemistry in the allenic and the phosphonate moiety.
M. Kalek, T. Johansson, M. Jezowska, J. Stawinski, Org. Lett., 2010, 12, 4702-4704.
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.
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.
Mn(OAc)3-mediated phosphinoyl radical addition followed by CuCN-catalyzed cyanation enables a double-functionalization reaction of alkenes under mild conditions to afford vicinal cyanophosphinoylation products.
P.-Z. Zhang, L. Zhang, J.-A. Li, A. Shoberu, J.-P. Zou, W. Zhang, Org. Lett., 2017, 19, 5537-5540.
An efficient phosphorylation of C(sp3)-H bonds of readily available methyl arenes with diaryl phosphinic acids proceeds efficiently under transition-metal-free reaction conditions via Bu4NI-catalyzed dehydrogenative coupling to provide valuable organophosphorus compounds.
B. Xiong, G. Wang, C. Zhou, Y. Liu, P. Zhang, K. Tang, J. Org. Chem., 2018, 83, 993-999.