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DOI: https://doi.org/10.6023/cjoc202601020

研究论文

桥联碳硼烷膦化合物的合成及其在大位阻Suzuki偶联反应中的应用

  • 张国英 ,
  • 张雪玥 ,
  • 苗金玲 ,
  • 刘广宁 ,
  • 王斌 ,
  • 聂永
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  • a济南大学化学化工学院,济南 250022;
    b济南大学智能材料与工程研究院,济南 250022

收稿日期: 2026-01-15

  修回日期: 2026-04-15

  网络出版日期: 2026-06-04

基金资助

山东省自然科学基金(No. ZR2022MB107)资助项目

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Synthesis of Bridged o-Carboranylphosphine Compounds and the Application in Sterically Demanding Suzuki Coupling Reaction

  • Zhang Guoying ,
  • Zhang Xueyue ,
  • Miao Jinling ,
  • Liu Guangning ,
  • Wang Bin ,
  • Nie Yong
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  • a School of Chemistry and Chemical Engineering, University of Jinan, Jinan, 250022;
    b Institute for Smart Materials & Engineering, University of Jinan, Jinan, 250022

Received date: 2026-01-15

  Revised date: 2026-04-15

  Online published: 2026-06-04

Supported by

Natural Science Foundation of Shandong Province (No. ZR2022MB107).

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摘要

本文报道桥联碳硼烷-二苯基膦化合物的合成、结构、稳定性及在金属催化偶联反应中的初步应用。邻碳硼烷锂盐与2-(二苯基膦基)苯甲醛反应,生成二苯基膦基碳硼烷甲醇1和双(二苯基膦基)碳硼烷二甲醇2. 化合物1发生羟基氯代反应生成化合物3,化合物1在空气中发生缓慢氧化生成相应的膦氧化合物4. 化合物1和2在空气中发生缓慢氧化,而氯代化合物3在相同条件下的氧化稳定性明显提高. 化合物1在碱性条件下,很快分解为邻碳硼烷和2-(二苯基膦)苯甲醛,相同条件下氯代产物3则缓慢发生分解. 通过谱学方法或元素分析、单晶X-射线衍射(1和2)和密度泛函理论(DFT)方法(1-3)研究了产物的组成和结构. 化合物3在钯催化的大位阻Suzuki偶联反应中展示了一定的潜力. 本文结果为桥联碳硼烷膦化合物用于有机功能分子的催化合成提供了新的可能.

关键词： 碳硼烷; 膦化合物; 合成; 稳定性; Suzuki偶联

本文引用格式

张国英 , 张雪玥 , 苗金玲 , 刘广宁 , 王斌 , 聂永 . 桥联碳硼烷膦化合物的合成及其在大位阻Suzuki偶联反应中的应用[J]. 有机化学, 0 : 0 . DOI: 10.6023/cjoc202601020

Abstract

The synthesis, structures, stabilities of bridged carboranyl-diphenylphosphine compounds and the preliminary applications in metal-catalyzed coupling reactions are reported. The lithium salt of o-carborane reacts with 2-(diphenylphosphino)benzaldehyde to produce bridged diphenylphosphinocarboranylmethanol 1 and bis(diphenylphosphino)-o-carboranylbismethanol 2. The chlorination reaction of compound 1 produces compound 3, and compound 1 undergoes slow oxidation in air to produce the corresponding phosphine oxide compound 4. Compounds 1 and 2 undergo slow oxidation in air, while the oxidation stabilities of the chlorinated compound 3 is significantly higher under the same conditions. Compound 1 readily decomposes into 2-(diphenylphosphine)benzaldehyde and o-carborane under basic conditions, whereas the chlorinated product 3 slowly decomposes under the same conditions. The structures of the products were studied by spectroscopic methods or elemental analysis, single crystal X-ray diffraction (1 and 2) and density functional theory methods (1-3). Compound 3 exhibits potential in palladium catalyzed sterically demanding Suzuki coupling reactions. These results provide new possibilities for bridged o-carboranylphosphine compounds in the catalytic synthesis of organic functional molecules.

Key words： carborane; phosphine compounds; synthesis; stability; Suzuki coupling

参考文献

[1] (a) Vogler, A., Kunkely, H. Coord. Chem. Rev. 2002, 230, 243.(b) Sutra, P.; Igau, A. Coord. Chem. Rev. 2016, 308, 97.(c) Coles, N.; Sofie Abels, A.; Leitl, J.; Wolf, R.; Grützmacher, H.; Müller, C. Coord. Chem. Rev. 2021, 432, 213729.
[2] (a) Demkowicz, S.; Rachon, J.; Daśko, M.; Kozak, W. RSC Adv. 2016, 6, 7101.(b) Dutartre, M.; Bayardon, J.; Jugé, S. Chem. Soc. Rev., 2016, 45, 5771.(c) Georgiadis, D.; Skoulikas, N.; Papakyriakou, A.; Stratikos, E. ACS Pharmacol. Transl. Sci. 2022, 5, 1228.
[3] (a) Tang, W.-J.; Zhang, X.-M. Chem. Rev. 2003, 103, 3029.(b) Li, W.-B; Zhang, J.-L. Acc. Chem. Res. 2024, 57, 489.(c) Cao, K.-N; Han, J.; Shen, H.-C; Yang, J.-F; Zhang, J.-L; Chen, F.-R. ACS Catal. 2024, 14, 5305.(d) He, D.-Y.; Xu, H.; Cao, P.-L.; Li, L.-Q.; Luo, Y.-L.; Mon, E.-E.; Peng, F.-Z.; Li, L.; Dang, Y.-F.; Shao, Z.-H. Angew. Chem. Int. Ed. 2025, 64, 1.(e) Liu, B.-X.; Feng, F.; Long, J.; Gu, S.-X. Chin. J. Chem. 2025, 43, 2228.
[4] (a) King, R. Chem. Rev. 2001, 101, 1119.(b) Grimes, R. N. Carboranes (Third Edition), Elsevier, London, 2016.
[5] (a) Hosmane, N. S., Boron science: New technologies and applications, CRC Press, Boca Raton: 2012.(b) Hosmane, N. S.; Eagling, R., Handbook of Boron Science: With Applications in Organometallics, Catalysis, Materials and Medicine, World Scientific, Singapore, 2018.
[6] (a) Núnñez, R.; Tarreés, M.; Ferrer-Ugalde, A.; Biani, F.; Teixidor, F. Chem. Rev. 2016, 116, 14307.(b) Tanaka, K. Dalton Trans., 2024, 53, 9240.(c) Ran, Z.-Y.; Zha, M.-M.; Shi, J.-Q.; Ji, L. Dyes Pigm. 2025, 232, 112484.
[7] (a) Ali, F.; Hosmane, N.; Zhu, Y.-H. Molecules 2020, 25, 828.(b) Marfavi, A.; Kavianpour, P.; Rendina, L. Nat. Rev. Chem. 2022, 6, 486.(c) Xu, H.; Liu, J.; Li, R.-X.; Lin, J.-J.; Gui, L.-J.; Wang, Y.-X.; Jin, Z.-Y.; Xia, W.; Liu, Y.-H.; Cheng, S.-J.; Yuan, Z.-W. Coord. Chem. Rev. 2024, 511, 215795.
[8] (a) Bauer, S.; Hey-Hawkins, Evamarie. In Boron Science: New technologies and applications, Ed.: Hosmane, N. S., CRC Press, Boca Raton, 2011.(b) Xu, Y.-L.; Yang, Y.-Z.; Liu, Y.-Z.; Li, Z.-H.; Wang, H.-D. Nat. Catal. 2023, 6, 16.(c) Bawari, D.; Dobrovetsky, R.; Toami, D.; Jaiswal, K. Nat. Chem. 2024, 16, 1261.(d) Vonnemann, C.; Engelage, E.; Ward, J.; Rissanen, K.; Keller, S.; Huber, S. Angew. Chem. Int. Ed. 2025, 64, 17.
[9] (a) Fisher, S.; Tomich, A.; Lovera, S.; Kleinsasser, J.; Guo, J.; Asay, M.; Nelson, H.; Lavallo, V. Chem. Rev. 2019, 119, 8262.(b) Qiu, Z.-Z.; Xie, Z.-W. Acc. Chem. Res. 2021, 54, 4065.(c) Cui, P.-F.; Lin, X.-R.; Jin, G.-X. J. Am. Chem. Soc. 2023, 145, 19440.
[10] (a) Lu, J.-Y.; Wan, H.; Zhang, J.-W.; Wang, Z.-X.; Li, Y.; Du, Y.-M.; Li, C.-Y.; Liu, Z.-T.; Liu, Z.-W.; Lu, J. Chem. Eur. J. 2016, 22, 17542.(b) Liu, L.-J.; C. W. Mak, T.; Zang, S.-Q. Chin. J. Chem. 2021, 39, 81.(c) Yuan, R.-Z.; Cui, P.-F.; Lin, Y.-J.; Jin, G.-X. Chin. J. Chem. 2023, 41, 307.(d) Li, P.; Yang, J.-Y.; Zeng, J.-Y.; Miao, S.-Q.; Fang, R.; Lu, J.; Lu, J.-Y. Org. Lett. 2024, 26, 8134.(e) Li, P.; Wen, C.; Li, X.; Lu, J.; Lu, J.-Y. Org. Lett. 2025, 27, 6848.(f) Li, P.; Qiu, Z.-H.; Lu, J.; Lu, J.-Y. Inorg. Chem. Front. 2025, 12, 1994.(g) Wu J; Cao K. Org. Biomol. Chem. 2025, 23, 370.(h) Huang, J.-H.; Cui, Y.; Wang, Z.-Y.; Zang, S.-Q. Acc. Chem. Res. 2025, 58, 1249.(i) Zhang, J.; Xie, Z.-W. Synthesis 2025, 57, 495.(g) Xie, H.-H.; Zhou, L.-J.; Cui, P.-F.; Zhang, W.-C. Coord. Chem. Rev. 2025, 542, 216803.(k) Ren, H.-Y.; Zhou, N.-N.; Ma, W.-L.; Tu, D.-S.; Lu, C.-S.; Yan, H. J. Am. Chem. Soc. 2026, 148, 4680.(l) Lei, C.; Lu, W.; Shen, T.-T.; Huang, M.; Wu, Y.-X.; Wei, D.-H.; Ma, Y-N.; Chen, X.-N. Nature Catal. 2026, 9, 161.(m) Liu, Y.-Y.; Luo, Q.-C.; Jin, P.-B.; Zheng, Y.-Z. Chin. J. Chem. 2025, 43, 131.
[11] Heying T.; Ager J.; Clark S.; Mangold H.; Hillman M.; Polak R.; Szymanski J Inorg.Chem. 1963, 2, 1089.
[12] (a) Alexander, R.; Schroeder, H. Inorg. Chem. 1963, 2, 1107.(b) Li, k.; Yao, Z,-J.; Deng, W. Curr. Org. Synth. 2016, 4, 504.
[13] (a) Popescu, A.; Teixidor, F.; Viñas, C. Coord. Chem. Rev. 2014, 269, 54.(b) Gál, D.; Szántai, L.; Buzsáki, D.; Kelemen, Z. Org. Lett. 2025, 27, 5637.
[14] (a) Crespo, O.; Gimeno, M.; Laguna, A. J. Organomet. Chem. 2009, 694, 1588.(b) Xiao, X.-Q.; Jin, G.-X. J. Organomet. Chem. 2011, 696, 504.
[15] (a) Wang, L.; Chen, R.-J.; Yan, J.-F.; Yuan, Y.-F. New J. Chem. 2023, 47, 16129.(b) Jia, C.-X.; Wang, F.; Zhao, P.; Li, Y.; Li, H.-Jun.; Zheng, X.; Duan, Z. Org. Lett. 2025, 27, 8892.
[16] (a) Zhang, Z.-Y.; Zhang, X.-P.; Yuan, J.; Yue, C.-D.; Meng, S.-X.; Chen, J.; Yu, G.-A.; Che, C.-M. Chem. Eur. J. 2020, 26, 5037.(b) Liu, J.-P.; Hu, Y.; Guo, R.; Meng, S.X.; Chen, J.; Yuan, J.; Yu, G.-A. J. Org. Chem. 2025, 90, 10957.
[17] (a) Godovikov, N.; Balema, V.; Rys, E. Russ. Chem. Rev. 1997, 66, 1017.(b) Tyutyunov, A.; Lyubimov, S.; Rys, E.; Verbitskaya, T.; Petrovskii, P.; Davankov, V.; Kalinin, V. Russ. Chem. Bull. 2008, 57, 2307.(c) Maulana, I.; Lonnecke, P.; Hey-Hawkins, E. Inorg. Chem. 2009, 48, 8638.(d) Yao, Z.-J.; Jin, G.-X. Coord. Chem. Rev. 2013, 257, 2522.(e) Lugo, C.; Moore, C.; Rheingold, A.; Lavallo, V. Inorg. Chem. 2015, 54, 2094.(f) Benton, A.; Watson, J.; Mansell, S.; Rosair, G.; Welch, A. J. Organomet. Chem. 2020, 907, 121057.(g) Zhang, J.; Xie, Z-W. Chem. Sci. 2021, 12, 1745.(h) Tao, G.-Y.; Yang, F.-C.; Zhang, L.-J.; Li, Y.; Duan, Z.; Mathey, F. Chin. Chem. Lett. 2021, 32, 194.(i) Sivaev, I.; Stogniy, M.; Bregadze, V. Coord. Chem. Rev. 2021, 436, 213795.(j) Chan, T.-L.; Zhang, J.; Xie, Z.-W. Dalton Trans., 2025, 54, 10946.(k) Jia, C.-X.; Wang.L.-L.; Duan, Z. Org. Lett. 2025, 27, 3139.(l) Chan, T.-L.; Zhang, J.; Xie, Z.-W. Inorg. Chem. 2026, 65, 7.(m) Alcántara M.; Hankins A.; Hussain S.; Guo J.; Sivakumar P.; Avalos M.; Wu G.; Zhou W.; Kulkarni A.; Ménard, G. J. Am. Chem. Soc.2026, ASAP, 10.1021/jacs.5c22507.
[18] (a) Furmanova, N.; Yanovskii, A.; Struchkov, Y.; Bregadze, V.; Godovikov, N.; Degtyarev, A.; Kabachnik, M. Russ. Chem. Bull. 1979, 28, 2167.(b) King, A.; Ferguson, G.; Britten, J.; Valliant, J. Inorg. Chem. 2004, 43, 3507.(c) Spokoyny, A.; Machan, C.; Clingerman, D.; Rosen, M.; Wiester, M.; Kennedy, R.; Stern, C.; Sarjeant, A.; Mirkin, C. Nat. Chem. 2011, 3, 590.(d) Rodríguez-Rey, J.; Esteban-Gómez, D.; Platas-Iglesias, C.; Sousa-Pedrares, A. Dalton Trans., 2019, 48, 486.
[19] Núñez R.; Viñas C.; Teixidor F.; Sillanpää R.; Kivekäs, R. J. Organomet. Chem. 1999, 592, 22.
[20] Nakamura H.; Aoyagi K.; Yamamoto Y. J. Am. Chem. Soc. 1998, 120, 1167
[21] Turner A.; Robertson H.; Borisenko K. Rankin,D.; Fox, M. Dalton Trans. 2005, 7, 1310.
[22] Li T.-R.; Zhang H.; Miao J.-L.; Xu C.-Y.; Nie Y.; Liu G.-N.; Sun G.-X.; Jiang X.-C.New J. Chem. 2023, 47, 18243.
[23] Frisch M. J.; Trucks G. W.; Schlegel H. B.; Scuseria G. E.; Robb M. A.; Cheeseman J. R.; Scalmani G.; Barone V.; Mennucci B.; Petersson G. A.; Nakatsuji H.; Caricato M.; Li X.; Hratchian H. P.; Izmaylov A. F.; Bloino J.; Zheng G.; Sonnenberg J. L.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Montgomery J. A.; Jr., Peralta, J. E.; Ogliaro, F.; Bearpark, M. Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford CT, 2009.
[24] Nakamura H.; Aoyagi K.; Yamamoto Y. J. Organomet. Chem. 1999, 574, 107.
[25] (a) Tang, W.-J.; Capacci, A. G.; Wei, X.-D.; Li, W.-J.; White, A.; Patel, N. D.; Savoie, J.; Gao, J. J.; Rodriguez, S.; Qu, B.; Haddad, N.; Lu, B. Z.; Krishnamurthy, D.; Yee, N. K.; Senanayake, C. H. Angew. Chem. Int. Ed. 2010, 49, 5879.(b) Zhao, Q.; Li, C.-X.; Senanayake, C. H.; Tang, W.-J. Chem. Eur. J. 2013, 19, 2261.(c) Fu, W.-Z.; Tang, W.-J. ACS Catal. 2016, 6, 4814.(d) Xu, G.-Q.; Senanayake, C.; Tang, W.-J.; Acc. Chem. Res. 2019, 52, 1101.
[26] Zhang Y.-Q.; Li Y.-S.; Pan B.-D.; Xu H.; Liang H.; Jiang X.-D.; Liu, B.-Y; Tse, M. K.; Qiu Li.-Q. ChemistrySelect 2019, 4, 5122.
[27] Tsang M.;Viñas, C.; Teixidor, F.; Planas, J.; Conde, N.; SanMartin, R.; Herrero, M.; Domínguez, E.; Lledós, A.; Vidossich, P.; Choquesillo-Lazarte, D. Inorg. Chem. 2014, 53, 9284.
[28] Lyubimov S.; Verbitskaya T.; Rys E.; Petrovskii P.; Il´in M.; Davankov V.; Kalinin V. Russ. Chem. Bull. 2010, 59, 1665.
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