Organic Chemistry Portal >
Reactions > Organic Synthesis Search

Categories: C-P Bond Formation >

Synthesis of phosphines

Recent Literature

A versatile and efficient Pd(OAc)2/1,1'-bis(diisopropylphosphino)ferrocene-catalyzed cross-coupling of thiols with aryl halides was developed. Aryl bromides and chlorides can be coupled to aliphatic and aromatic thiols - the widest substrate scope of any reported to date. This catalyst system also enables the coupling of secondary phosphines with aryl halides.
M. Murata, S. L. Buchwald, Tetrahedron, 2004, 60, 7397-7403.

Acylphosphines are inert to air and moisture. A palladium-catalyzed C-P bond formation reaction using acylphosphines as phosphination reagents shows practicable reactivity with ArBr and ArOTf to afford trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance.
X. Chen, H. Wu, R. Yu, H. Zhu, Z. Wang, J. Org. Chem., 2021, 86, 8987-8996.

A series of novel functionalized, hemilabile phosphines have been prepared from diaryl­phosphines using several synthetic methodologies - including alkylation of lithium diarylphosphide or (di­arylphosphino)borane adducts with functionalized halogenoalkanes and the photochemical hydrophosphination of suitable functionalized allyl or vinyl derivatives using white light.
M. V. Jiménez, J. J. Pérez-Torrente, M. I. Bartolomé, L. A. Oro, Synthesis, 2009, 1916-1922.

Phosphine oxides are selectively reduced to phoshphines in the presence of other reducible functional groups such as ketones, esters, and olefins using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes. Based on this transformation, an efficient one pot reduction/phosphination domino sequence generates functionalized aromatic and aliphatic phosphines in good yields.
Y. Li, S. Das, S. Zhou, K. Junge, M. Beller, J. Am. Chem. Soc., 2012, 134, 9727-9732.

CuCl2 catalyzes a C(sp2)-P bond forming reaction of aryl iodides and bromides with an acylphosphine as the phosphorus source to provide triarylphosphines in very good yield. A preliminary study of the mechanism was carried out and found that a radical intermediate is not involved.
M. Xu, Z. Zhu, H. Yi, H. Zhu, Z. Wang, Synthesis, 2023, 55, 2586-2594.

A convenient and scalable method provides diverse trifluoromethylphosphines via direct radical trifluoromethylation of phosphine chlorides with CF3Br in the presence of zinc powder.
D. Peng, S. Zhang, W. Fan, Y. Wen, S. Li, Org. Lett., 2023, 25, 3892-3897.

Triazole-based monophosphine ligands have been prepared via efficient cycloadditions. Palladium complexes derived from these ligands are highly active catalysts for Suzuki-Miyaura coupling and amination reactions of aryl chlorides.
D. Liu, W. Gao, Q. Dai, X. Zhang, Org. Lett., 2005, 7, 4907-4910.

A highly stereoselective asymmetric 1,4-addition of diarylphosphines to α,β-unsaturated aldehydes catalyzed by a bis(phosphine) pincer-Pd complex enables the synthesis of chiral phosphines with excellent stereoselectivity under mild conditions.
Y.-R. Chen, W.-L. Duan, Org. Lett., 2011, 13, 5824-5826.

Palladium and Raney nickel catalyze the methanolysis of strongly complexed borane-amine adducts. The method is applicable to primary, secondary, tertiary, and aromatic amines, and the mildness of the reaction conditions allows preservation of otherwise labile functional groups.
A [Cu(OH)•TMEDA]2Cl2 catalyzed tandem reaction allows the synthesis of a series of sterically and electronically divergent phenacyl tertiary phosphine-boranes.
G. Kumaraswamy, G. V. Rao, A. N. Murthy, B. Sridhar, Synlett, 2009, 1180-1184.


C-P activation of phosphonium salts enables a "group-substitution" synthesis of trivalent phosphines. An alkylation of phosphines to provide phosphonium salts is followed by a Pd-catalyzed "de-arylation" via C-P activation and transfer hydrogenation. With this method, a series of trivalent phosphines were prepared from commercially available triarylphosphines.
M. Lei, X. Chen, Y. Wang, L. Zhang, H. Zhu, Z. Wang, Org. Lett., 2022, 24, 2868-2872.

A stereoselective hydrophosphination reaction of alkynes with diphenylphosphane has been developed. The reaction is mediated by a cobalt catalyst and butyllithium.
H. Ohmiya, H. Yorimitsu, K. Oshima, Angew. Chem. Int. Ed., 2005, 44, 2368-2370.

A catalytic amount of a Brønsted base mediates a stereoselective diphosphination of terminal alkynes with diphosphanes to deliver the corresponding (E)-1,2-diphosphinoethenes in good yields. This reaction offers a good alternative to precedented transition-metal-catalyzed or radical-promoted approaches to the 1,2-diphosphinoethene framework of potent interest in catalysis and coordination chemistry.
Y. Okugawa, K. Hirano, M. Miura, Org. Lett., 2017, 19, 2973-2976.

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.