基于膦杂碗烯的螺旋手性单膦配体合成

doi:10.6023/cjoc202510033

基于膦杂碗烯的螺旋手性单膦配体合成

王明慧^†, 刘祖恋^†, 杨德玺, 苏嘉琪, 徐嘉麒, 付海燕, 李瑞祥, 陈华, 郑学丽^*, 薛卫超^*

四川大学化学学院成都 610064

收稿日期:2025-10-30 修回日期:2025-12-12
作者简介:^†共同第一作者
基金资助:
四川省科技厅自然科学基金(No. 2024YFFK0016, 2024ZYD009)和中央高校基本科研业务费(No. 20822041J4097, 0082604151502)资助项目.

Synthesis of Phosphangulene-Derived Chiral Monophosphorus Ligands

Wang Minghui^†, Liu Zulian^†, Yang Dexi, Su Jiaqi, Xu Jiaqi, Fu Haiyan, Li Ruixiang, Chen Hua, Zheng Xueli^*, Xue Weichao^*

College of Chemistry, Sichuan University, Chengdu 610064

Received:2025-10-30 Revised:2025-12-12
Contact: ^*E-mail: zhengxueli@scu.edu.cn; weichaoxue@scu.edu.cn
About author:^†(These authors contributed equally to this work).
Supported by:
Project supported by the Sichuan Provincial Natural Science Foundation (No. 2024YFFK0016, 2024ZYD0099) and the Fundamental Research Funds for the Central Universities (No. 20822041J4097, 0082604151502).

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摘要/Abstract

新型手性膦配体的开发一直是有机合成领域的研究重点之一. 本文报道了一种螺旋手性单膦配体的高效合成策略. 基于该方法, 我们成功制备了四种结构新颖的具有螺旋手性的碗状单膦配体, 并系统评估了它们在钯催化的C-C键与C-N键构建反应中作为配体的性能. 通过高效液相色谱(HPLC)拆分, 获得了单一手性的配体. 尽管在上述反应中未能实现理想的对映选择性控制, 但该类配体所展现的独特螺旋手性空腔与优异的配位活性, 表明其在其他不对称催化体系中具有进一步开发与应用的潜力.

关键词: 膦配体, 螺旋手性, 碗状结构, 催化反应

The development of novel chiral phosphine ligands is a key area of research in organic synthesis. In this study, we report an efficient synthetic method for the preparation of helically chiral monophosphorus ligands. Using this approach, four structurally distinct, helically chiral, bowl-shaped monophosphorus ligands were successfully synthesized. Their catalytic activities were systematically evaluated in palladium-catalyzed C-C and C-N bond-forming reactions. Enantiopure ligands were obtained via HPLC resolution. Although these reactions did not achieve high enantiocontrol, the ligands demonstrated a unique helical chiral cavity and excellent catalytic activity. These findings suggest that this class of compounds warrants further exploration in other asymmetric catalytic reactions.

Key words: Phosphorus ligand, Helically chiral, Bowl shape, Catalysis

引用此文

王明慧, 刘祖恋, 杨德玺, 苏嘉琪, 徐嘉麒, 付海燕, 李瑞祥, 陈华, 郑学丽, 薛卫超. 基于膦杂碗烯的螺旋手性单膦配体合成[J]. 有机化学, doi: 10.6023/cjoc202510033.

Wang Minghui, Liu Zulian, Yang Dexi, Su Jiaqi, Xu Jiaqi, Fu Haiyan, Li Ruixiang, Chen Hua, Zheng Xueli, Xue Weichao. Synthesis of Phosphangulene-Derived Chiral Monophosphorus Ligands[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202510033.

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参考文献

[1] Fu W.-Z.; Tang W.-J.ACS Catal. 2016, 6, 4814.
[2] Rojo P.; Riera A.; Verdaguer X.Coord. Chem. Rev. 2023, 489, 215192.
[3] Imamoto T.Chem. Rev. 2024, 124, 8657.
[4] Cabré A.; Riera A.; Verdaguer X.Acc. Chem. Res. 2020, 53, 676.
[5] Dutartre M.; Bayardon J.; Jugé S.Chem. Soc. Rev. 2016, 45, 5771.
[6] Bandaru S. S.M.; Shah, J.; Bhilare, S.; Schulzke, C.; Kapdi, A. R.; Roger, J.; Hierso, J.-C.Coord. Chem. Rev. 2023, 491, 215250.
[7] Pellissier H.Coord. Chem. Rev. 2023, 482, 215079.
[8] Iwamoto H.; Ozawa Y.; Hayashi Y.; Imamoto T.; Ito H.J. Am. Chem. Soc. 2022, 144, 10483.
[9] Li C.-X.; Wan F.; Chen Y.; Peng H.-N.; Tang W.-J.; Yu S.; McWilliams, J. C.; Mustakis, J.; Samp, L.; Maguire, R. J.Angew. Chem. Int. Ed. 2019, 58, 13573.
[10] Zhou H.; Wang W.-H.; Fu Y.; Xie J.-H.; Shi W.-J.; Wang L.-X.; Zhou Q.-L.J. Org. Chem. 2003, 68, 1582.
[11] Mondal A.; Thiel N. O.; Dorel R.; Feringa B. L.Nat. Catal. 2022, 5, 10.
[12] Wu J.-H.; Tan J.-P.; Zheng J.-Y.; He J.-J.; Song Z.-L.; Su Z.-S.; Wang T.-L.Angew. Chem. Int. Ed. 2023, 62, e202215720.
[13] Lv X.-L.; Wang M.-Y.; Zhao Y.; Shi Z.-Z.J. Am. Chem. Soc. 2024, 146, 3483.
[14] Dong K.-W.; Sang R.; Fang X.-J.; Franke R.; Spannenberg A.; Neumann H.; Jackstell R.; Beller M.Angew. Chem. Int. Ed. 2017, 56, 5267.
[15] Pye P. J.; Rossen K.; Reamer R. A.; Tsou N. N.; Volante R. P.; Reider P. J.J. Am. Chem. Soc. 1997, 119, 6207.
[16] El Abed, R.; Aloui, F.; Genêt, J.-P.; Ben Hassine, B.; Marinetti, A.J. Organomet. Chem. 2007, 692, 1156.
[17] Wu J.-H.; Fang S.-Q.; Zheng X.-T.; He J.-J.; Ma Y.; Su Z.-S.; Wang T.-L.Angew. Chem. Int. Ed. 2023, 62, e202309515.
[18] Krebs F. C.; Larsen P. S.; Larsen J.; Jacobsen C. S.; Boutton C.; Thorup N.J. Am. Chem. Soc. 1997, 119, 1208.
[19] Heskia A.; Maris T.; Wuest J. D.Acc. Chem. Res. 2020, 53, 2472.
[20] Schaub T. A.; Zolnhofer E. M.; Halter D. P.; Shubina T. E.; Hampel F.; Meyer K.; Kivala M.Angew. Chem. Int. Ed. 2016, 55, 13597.
[21] Saito M.; Shinokubo H.; Sakurai H.Mater. Chem. Front. 2018, 2, 635.
[22] Yang Y.; Ronson T. K.; Lu Z.-F.; Zheng J.-Y.; Vanthuyne N.; Martinez A.; Nitschke J. R.Nat. Commun. 2021, 12, 4079.
[23] Yamamura M.; Saito T.; Nabeshima T.J. Am. Chem. Soc. 2014, 136, 14299.
[24] Vandeputte E.; Antonetti E.; Nava P.; Dutasta J.-P.; Chatelet B.; Moraleda D.; Nuel D.; Giordano L.; Martinez A.J. Org. Chem. 2024, 89, 5314.
[25] Trost B. M.;Van Vranken, D. L.Chem. Rev. 1996, 96, 395.
[26] Liu M.-M.; Zhang X.-T.; Bao R.-R.; Xiao F.-T.; Cen S.-Y.; Zhang Z.-P.Org. Lett. 2023, 25, 5946.
[27] Prabagar B.; Yang Y.-Q.; Shi Z.-Z.Chem. Soc. Rev. 2021, 50, 11249.
[28] Gao X.; Wu B.; Huang W.-X.; Chen M.-W.; Zhou Y.-G.Angew. Chem. Int. Ed. 2015, 54, 11956.