Categories: C-P Bond Formation >
Synthesis of phosphine oxides
An efficient Ni-catalyzed coupling of a wide range of arylboronic acids with H-phosphites, H-phosphinate esters, and H-phosphine oxides provides various aryl-phosphorus compounds, including valuable triarylphosphine oxides, in very good yield.
G. Hu, W. Chen, T. Fu, Z. Peng, H. Qiao, Y. Gao, Y. Zhao, Org. Lett., 2013, 15, 5363-5365.
A copper-catalyzed reaction of phosphorus nucleophiles with diaryliodonium salts at room temperature delivers products of a P-C bond formation in high yields within a short reaction time of 10 min. The method can be easily adapted to large-scale preparations. With unsymmetrical iodonium salts, nucleophilic substitution occurs preferentially on the sterically hindered aromatic ring or the more electron-deficient ring.
J. Xu, P. Zhang, Y. Gao, Y. Chen, G. Tang, Y. Zhao, J. Org. Chem., 2013, 78, 8176-8183.
A palladium-catalyzed C-P bond formation between dichloroheterocycles and secondary phosphine oxides provides heterocyclic compounds bearing two tertiary phosphine oxides in good yields. Extension of the methodology to monohalohetarenes and monohaloarenes was successfully carried out; the steric and electronic properties of the halides were varied widely.
G. G. Zajkirova, D: Y. Mladentsev, N. E. Borisova, Synthesis, 2019, 51, 2379-2386.
A broad range of aryl iodides are efficiently coupled with secondary phosphine oxides using low loadings of a catalyst formed in situ from tris(dibenzylideneacetone)dipalladium and Xantphos.
A. J. Bloomfield, S. B. Herzon, Org. Lett., 2012, 14, 4370-4373.
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 Pd/Xiao-Phos-catalyzed cross-coupling reaction of easily accessible secondary phosphine oxides and aryl bromides provides rapid access to P-chiral phosphine oxides. The reaction proceeds efficiently with a wide array of reaction partners to deliver various tertiary phosphine oxides.
Q. Dai, W. Li, Z. Li, J. Zhang, J. Am. Chem. Soc., 2019, 141, 20556-20564.
A Cu-catalyzed enantioselective arylation of secondary phosphine oxides with diaryliodonium salts enables the synthesis of tertiary phosphine oxides with high enantiomeric excess. The process converts a wide range of substrates and leads to products that are well-established P-chiral catalysts and ligands.
R. Beaud, R. J. Phipps, M. J. Gaunt, J. Am. Chem. Soc., 2016, 138, 13183-13186.
NiCl2 • 6 H2O/Zn catalyzes the cross-coupling of aryl halides with diphenylphosphine oxide (Ph2P(O)H) and (RP)-(−)-menthyl benzylphosphinate in water under relatively mild conditions.
X. Zhang, H. Liu, X. Hu, G. Tang, J. Zhu, Y. Zhao, Org. Lett., 2011, 13, 3478-3481.
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.
In a decarboxylative cross-coupling of alkynyl acids in the presence of 10 mol % of CuCl without added ligand, base, and additive, various alkynyl acids reacted with H-phosphine oxides to afford E-alkenylphosphine oxides with operational simplicity, broad substrate scope, and absolute stereoselectivity.
G. Hu, Y. Gao, Y. Zhao, Org. Lett., 2014, 16, 4464-4467.
A radical-promoted decarboxylation enables a transition-metal-free phosphorylation of cinnamic acids with P(O)H compounds under mild conditions. This method provides simple, efficient, and versatile access to a broad range of valuable (E)-alkenylphosphine oxides in good yields.
L. Liu, D. Zhou, J. Dong, Y. Zhou, S.-F. Yin, L.-B. Han, J. Org. Chem., 2018, 83, 4190-4196.
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.
A silver-free palladium-catalyzed dehydrogenative phosphorylation of terminal alkynes with hydrogen phosphine oxides produces the corresponding value-added alkynylphosphine oxides in very good yields. This reaction could be easily conducted at gram scales without any decrease of efficiency.
J.-Q. Zhang, T. Chen, J.-S. Zhang, L.-B. Han, Org. Lett., 2017, 19, 4692-4695.
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 direct and convenient coupling of propargylic substrates with diphenylphosphine oxide in the presence of Tf2O and 2,6-lutidine provides attractive allenylphosphoryl skeletons with high atom and step economy under metal free conditions.
C.-H. Yang, H. Fan, H. Li, S. Hou, X. Sun, D. Luo, Y. Zhang, Z. Yang, J. Chang, Org. Lett., 2019, 21, 9438-9441.
A facile and efficient copper-catalyzed direct C-P cross-coupling of unprotected propargylic alcohols with P(O)H compounds provides valuable allenylphosphoryl frameworks with operational simplicity and high step- and atom-economy under ligand-, base-, and additive-free conditions.
G. Hu, C. Shan, W. Chen, P. Xu, Y. Gao, Y. Zhao, Org. Lett., 2016, 18, 6066-6069.
An efficient catalyst- and solvent-free addition of secondary phosphine chalcogenides to diverse aldehydes enables an almost quantitative synthesis of tertiary α-hydroxyphosphine chalcogenides under mild conditions (20-52 °C, from 10 min to 5 h).
N. K. Gusarova, N. I. Ivanova, P. A. Volkov, K. O. Khrapova, L. I. Larina, V. I. Smirnov, T. N. Borodina, B. A. Trofimov, Synthesis, 2015, 47, 1611-1622.
A general synthetic procedure using 2 eq. of BSA as silylating agent provides H-α-hydroxyphosphinates in very good yields in short times via Abramov reaction. The H-α-hydroxyphosphinates can easily be purified and obtained.
J. Dussart, J. Deschamp, M. Monteil, O. Gager, E. Migianu-Griffoni, M. Lecouvey, Synthesis, 2019, 51, 421-432.
A visible light-mediated photocatalytic decarboxylative oxyphosphorylation of cinnamic acids with diarylphosphine oxides provides the corresponding β-ketophosphine oxides under mild conditions.
H.-F. Qian, C.-K. Li, Z.-H. Zhou, Z.-K. Tao, A. Shoberu, J.-P. Zou, Org. Lett., 2018, 20, 5947-5951.
An asymmetric addition of diarylphosphines to β-substituted enones under mild conditions using a chiral pincer-palladium allows the synthesis of chiral phosphines with excellent enantioselectivity.
J.-J. Feng, X.-F. Chen, M. Shi, W.-L. Duan, J. Am. Chem. Soc., 2010, 132, 5562-5563.
Chiral PCN pincer Pd(II) complexes were examined as enantioselective catalysts for the hydrophosphination of enones. Hydrophosphination of 2-alkenoylarenes with diphenylphosphine followed by oxidation with hydrogen peroxide afforded the corresponding chiral phosphine oxides in good yields with very good enantioselectivities.
X.-Q. Hao, J.-J. Huang, T. Wang, J. Lv, J.-F. Gong, M.-P. Song, J. Org. Chem., 2014, 79, 9512-9530.
Several E and Z configured α,β-unsaturated carbonyl and carboxyl acceptors (including imides) as well as nitroalkenes participate in a palladium(II)-catalyzed conjugate transfer of diphenyl-, dicyclohexyl-, and di-tert-butylphosphinyl groups from silylphosphines in high chemical yields.
V. T. Trepohl, S. Mori, K. Itami, M. Oestreich, Org. Lett., 2009, 11, 1091-1094.
A Pd(OAc)2/Xantphos-based catalyst enabled a deprotonative cross-coupling process between benzyl diphenyl or dicyclohexyl phosphine oxide derivatives and aryl bromides to prepare diarylmethyl phosphine oxides in very good yields.
S. Montel, T. Jia, P. J. Walsh, Org. Lett., 2014, 16, 130-133.