REVIEW

Recent Advances in the Double Hydrophosphination and Hydrophosphinylation of Alkynes

  • Dongting Cheng ,
  • Nengbo Zhu ,
  • Hongli Bao
Expand
  • aCollege of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian Province, 350007;
    bFujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, State Key Laboratory of Structural Chemistry, Fuzhou, Fujian Province, 350002;
    cFujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian Province, 350002;
    dCollege of Chemistry, Fuzhou University, Fuzhou, Fujian Province, 350108

Received date: 2026-03-05

  Revised date: 2026-04-18

  Online published: 2026-05-19

Supported by

National Natural Science Foundation of China (No. 22225107) and the Natural Science Foundation of Fujian Province (No. 2025J01249)

Abstract

Bidentate phosphine ligands play an important role in catalysis because they can cooperatively regulate the electronic properties and steric environment of transition metal centers. In recent years, significant progress has been made in methods for constructing various diphosphine ligands through the double hydrophosphination (hydrophosphinylation) of alkynes. Considerable advances have been achieved in selectivity control and substrate scope. This review summarizes recent progress in alkyne double hydrophosphination (hydrophosphinylation) from three aspects: transition metal-catalyzed and template-promoted systems, non-transition-metal systems, and radical and photocatalytic systems. The regioselectivity and stereoselectivity in the formation of 1,1- and 1,2-diphosphine frameworks are analyzed. Key issues, such as catalyst deactivation, are also discussed. Finally, the future prospects of this field are outlined.

Cite this article

Dongting Cheng , Nengbo Zhu , Hongli Bao . Recent Advances in the Double Hydrophosphination and Hydrophosphinylation of Alkynes[J]. Chinese Journal of Organic Chemistry, 2026 : 3007 . DOI: 10.6023/cjoc202603007

References

[1] Koshti V.; Gaikwad S.; Chikkali S. H.,Coord. Chem. Rev. 2014, 265, 52.
[2] Kawaguchi S.; Ogawa A.,Synlett. 2013, 24, 2199.
[3] Montchamp J. L.,Acc. Chem. Res. 2014, 47, 77.
[4] Zhao D. P.; Wang R.,Chem. Soc. Rev. 2012, 41, 2095.
[5] Hooper J. F.; Young R. D.; Weller A. S.; Willis M. C.,Chem. Eur. J. 2013, 19, 3125.
[6] Rodriguez-Ruiz, V.; Carlino, R.; Bezzenine-Lafollée, S.; Gil, R.; Prim, D.; Schulz, E.; Hannedouche, J.,Dalton Trans. 2015, 44, 12029.
[7] Birkholz M. N.; Freixa Z.; van Leeuwen, P. W. N. M.,Chem. Soc. Rev. 2009, 38, 1099.
[8] Chaplin A. B.; Hooper J. F.; Weller A. S.; Willis M. C.,J. Am. Chem. Soc. 2012, 134, 4885.
[9] Pernik I.; Hooper J. F.; Chaplin A. B.; Weller A. S.; Willis M. C.,ACS Catal. 2012, 2, 2779.
[10] Hofmann P.; Meier C.; Hiller W.; Heckel M.; Riede J.; Schmidt M. U.,J. Organomet. Chem. 1995, 490, 51.
[11] Standley E. A.; Tasker S. Z.; Jamison T. F.,Nature 2014, 504, 299.
[12] Powers I. G.; Uyeda C.,ACS Catal. 2017, 7, 936.
[13] Hewertson W.; Watson H. R.,J. Chem. Soc. 1962, 1490.
[14] Honaker M. T.; Sandefur B. J.; Hargett J. L.; McDaniel, A. L.; Salvatore, R. N.,Tetrahedron Lett. 2003, 44, 8373.
[15] Tsvetkov E. N.; Bondarenko N. A.; Malakhova I. G.; Kabachnik M. I.,Synthesis (Stuttg.). 1986, 198.
[16] Honaker M. T.; Salvatore R. N.,Phosphorus Sulfur Silicon Relat. Elem. 2004, 179, 277.
[17] Lau S.; Hood T. M.; Webster R. L.,ACS Catal. 2022, 12, 10939.
[18] Alonso F.; Beletskaya I. P.; Yus M.,Chem. Rev. 2004, 104, 3079.
[19] Wauters I.; Debrouwer W.; Stevens C. V.,Beilstein J. Org. Chem. 2014, 10, 1064.
[20] Baillie C.; Xiao J. L.,Curr. Org. Chem. 2003, 7, 477.
[21] Sato A.; Yorimitsu H.; Oshima K.,Angew. Chem. Int. Ed. 2005, 44, 1694.
[22] Liu Y. J.; Zhang K. K.; Tian R. Q.; Duan Z.; Mathey F.,Org. Lett. 2020, 22, 6972.
[23] Hirano K.; Miura M.,Tetrahedron Lett. 2017, 58, 4317.
[24] Rosenberg L.,ACS Catal. 2013, 3, 2845.
[25] Moglie Y.;González-Soria, M. J.; Martín-García, I.; Radivoy, G.; Alonso, F.,Green Chem. 2016, 18, 4896.
[26] Nune S. K.; Tanaka M.,Chem. Commun. 2007, 38, 2858.
[27] Yoshimura A.; Saga Y.; Sato Y.; Ogawa A.; Chen T. Q.; Han L. B.,Tetrahedron Lett. 2016, 57, 3382.
[28] Deprèle S.; Montchamp J. L.,J. Am. Chem. Soc. 2002, 124, 9386.
[29] Kamitani M.; Itazaki M.; Tamiya C.; Nakaiawa H.,J. Am. Chem. Soc. 2012, 134, 11932.
[30] Blackaby W. J.M.; Neale, S. E.; Isaac, C. J.; Sabater, S.; Macgregor, S. A.; Whittlesey, M. K.,ChemCatChem 2019, 11, 1893.
[31] Sun T. J.; Sun G. Y.; Sun W.; Peng X. S.; Liao J.; You Y.; Yuan W. C.,Chin. J. Org. Chem. 2024, 44, 3647 (in Chinese)
(孙婷珈, 孙国银, 孙威, 彭雪松, 廖娟, 游勇, 袁伟成, 有机化学, 2024, 44, 3647).
[32] Meißner A.; Alberico E.; Drexler H. J.; Baumann W.; Heller D.,Catal. Sci. Technol. 2014, 4, 3409.
[33] Di Giuseppe, A.; De Luca, R.; Castarlenas, R.; Pérez-Torrente, J. J.; Crucianelli, M.; Oro, L. A.,Chem. Commun. 2016, 52, 5554.
[34] Waterman R.,Curr. Org. Chem. 2008, 12, 1322.
[35] Allen A.; Ma L.; Lin W. B.,Tetrahedron Lett. 2002, 43, 3707.
[36] Tang L.; Zhang Y.; Ding L.; Li Y.; Mok K. F.; Yeo W. C.; Leung P. H.,Tetrahedron Lett. 2007, 48, 33.
[37] Zhang Y.; Tang L.; Ding Y.; Chua J.-H.; Li Y.; Yuan M.; Leung P. H.,Tetrahedron Lett. 2008, 49, 1762.
[38] Bange C. A.; Waterman R.,ACS Catal. 2016, 6, 6413.
[39] Wicht D. K.; Kourkine I. V.; Ivan K.; Glueck D. S.,Organometallics 1999, 18, 5381.
[40] Liu M.; Sun C.; Hang F.; Sun N.; Chen D.,Dalton Trans. 2014, 43, 4813.
[41] Ackley B. J.; Pagano J. K.; Waterman R.,Chem. Commun. 2018, 54, 2774.
[42] Yuan J.; Zhu L. Z.; Zhang J. Y.; Li J. F.; Cui C. M.,Organometallics 2017, 36, 455.
[43] Jin L.; Hao W.; Xu J.; Sun N.; Hu B.; Shen Z.; Mo W.; Hu X.,Chem. Commun. 2017, 53, 4124.
[44] Bookham J. L.; Mcfarlane W.; Thornton-Pett, M.; Jones, S.,J. Chem. Soc., Dalton Trans. 1990, 12, 3621.
[45] Whitelaw M. T.; Banerjee S.; Kennedy A. R.; Teijlingen A. V.; Tuttle T.; Mulvey R. E.,Cell Rep. Phys. Sci. 2022, 3, 100942.
[46] Bookham J. L.; Smithies D. M.; Wright A.; Thornton-Pett, M.; McFarlane, W.,J. Chem. Soc., Dalton Trans. 1998, 37, 811.
[47] Mitchell T. N.; Heesche K.,J. Organomet. Chem. 1991, 409, 163.
[48] Bookham J. L.; Smithies D. M.,J. Organomet. Chem. 1999, 577, 305.
[49] Merino P.;Marqués-López, E.; Herrera, R. P.,Adv. Synth. Catal. 2008, 350, 1195.
[50] Coles N. T.; Mahon M. F.; Webster R. L.,Chem. Commun. 2018, 54, 10443.
[51] Banerjee I.; Harinath A.; Panda T. K.,Eur. J. Inorg. Chem. 2019, 2019, 2224.
[52] Salin A. V.; Il’in A. V.; Faskhutdinov R. I.; Fayzullin R. R.,Tetrahedron 2019, 75, 2676.
[53] Parveen D.; Mittal S.; Shrivas R.; Pathak B.; Roy D. K.,Chem. Eur. J. 2025, 31, e202500002.
[54] Tolpygin A. O.; Cherkasov A. V.; Fukin G. K.; Kovylina T. A.; Lyssenko K. A.; Trifonov A. A.,Eur. J. Inorg. Chem. 2019, 2019, 4289.
[55] Hu H. F.; Cui C. M.,Organometallics 2012, 31, 1208.
[56] Basiouny M. M.I.; Dollard, D. A.; Schmidt, J. A. R.,ACS Catal. 2019, 9, 7143.
[57] Takaki K.; Komeyama K.; Kobayashi D.; Kawabata T.; Takehira K.,J. Alloys Compd. 2006, 408, 432.
[58] Yuan J.; Hu H. F.; Cui C. M.,Chem. Eur. J. 2016, 22, 5778.
[59] Guo H. Q.; Yoshimura A.; Chen T. Q.; Saga Y.; Han L. B.,Green Chem. 2017, 19, 1502.
[60] Yoshimura A.JP 2018076264 A. 2018.
[61] Zhu D. Y.; Dang H. X.; Wang S. H.CN 120098034 A, 2025.
Outlines

/