镍催化芳基/烯丙基交叉亲电偶联反应制备烯丙基取代芳基硼酸酯

doi:10.6023/cjoc202603013

有机化学

研究论文

镍催化芳基/烯丙基交叉亲电偶联反应制备烯丙基取代芳基硼酸酯

刘涛波^a, 刘猛^a, 刘鑫东^a, 韩梅兰^a, 徐光利^*,a,b,c, 韩鸿萍^*,a,b,c

^a青海师范大学化学化工学院西宁 810000;
^b高原科学与可持续发展研究院西宁 810000;
^c青海省环境功能材料先进技术与应用重点实验室西宁 810016

收稿日期:2026-03-10 修回日期:2026-07-06 发布日期:2026-09-14
基金资助:
青海省自然科学基金(No. 2024-ZJ-998)资助项目.

Nickel-Catalyzed Aryl-Allyl Cross-Electrophile Coupling for the Synthesis of Allyl-Substituted Aryl Boronates

Liu Taobo^a, Liu Meng^a, Liu Xindong^a, Han Meilan^a, Xu Guangli^*,a,b,c, Han Hongping^*,a,b,c

^aCollege of Chemistry & Chemical Engineering, Qinghai Normal University, Xining 810000;
^bAcademy of Plateau Science and Sustainability, Xining 810000, P. R. China;
^cQinghai Key Laboratory of Advanced Technology and Application of Environmental Functional Materials, Xining 810016, China

Received:2026-03-10 Revised:2026-07-06 Published:2026-09-14
Supported by:
Natural Science Foundation of Qinghai Province (No. 2024-ZJ-998).

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摘要/Abstract

报道了一种以烯丙醇与硼酸酯取代芳基三氟甲磺酸酯为反应底物,依托镍催化芳基-烯丙基交叉亲电偶联策略,高效构筑烯丙基取代芳基硼酸酯分子骨架的合成新路径。该体系条件温和,官能团兼容性好;克级制备实验证明其具备工业化潜力。所得产物可经Suzuki、Chan-Lam偶联衍生为多样复杂分子,并可转化为各类活性官能团,展现出优良的合成应用价值。

关键词: 镍催化, 还原偶联, 烯丙醇, 烯丙基取代芳基硼酸酯

A novel synthetic strategy for the efficient assembly of allyl-substituted aryl boronate scaffolds via nickel-catalyzed aryl-allyl cross-electrophile coupling is reported, with allylic alcohols and boronate-functionalized aryl triflates serving as starting materials. This catalytic system proceeds under mild conditions and exhibits broad functional group tolerance. Gram-scale preparation experiments verify its potential for industrial translation. The resulting products can be elaborated into diverse sophisticated molecules through Suzuki-Miyaura and Chan-Lam couplings, and readily converted to a wide range of reactive functional groups, thus demonstrating outstanding synthetic utility.

Key words: Nickel-Catalyzed, Reductive coupling, Allyl alcohols, Allyl-substituted arylboronates

引用此文

刘涛波, 刘猛, 刘鑫东, 韩梅兰, 徐光利, 韩鸿萍. 镍催化芳基/烯丙基交叉亲电偶联反应制备烯丙基取代芳基硼酸酯[J]. 有机化学, doi: 10.6023/cjoc202603013.

Liu Taobo, Liu Meng, Liu Xindong, Han Meilan, Xu Guangli, Han Hongping. Nickel-Catalyzed Aryl-Allyl Cross-Electrophile Coupling for the Synthesis of Allyl-Substituted Aryl Boronates[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202603013.

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[1] (a) Yang, Y.; Buchwald, S. L. J. Am. Chem. Soc., 2013, 135, 10642.
(b) Hu Y. C.; Min X. T.; Ji D. W.; Chen, Q. A. Trends Chem.2022, 4, 658.
[2] (a) Botta B.; Monache G. D.; Menendez P.; Boffi, A. Trends Pharmacol. Sci.2005, 26, 606.
(b) Botta B.; Vitali A.; Menendez P.; Misiti D.; Monache G. D.; Curr. Med. Chem.2005, 12, 713.
[3] (a) Mishra, N. K.; Sharma, S.; Park, J.; Han, S.; Kim, I. S.ACS Catal. 2017, 7, 2821.
(b) Tran M. K.; Ready, J. M. Angew. Chem., Int. Ed.,2024, 63, e202407824.
[4] (a) Yuan C.; Zhang W. Org. Lett.2025, 27, 3877.
(b) Hu A. M.; Tu J. L.; Wang K.; Yin J.; Guo L.; Yang C., Xia, W. Org. Lett.2024, 26, 8572.
[5] (a) Hamilton J. Y.; Hauser N.; Sarlah D.; Carreira, E. M. Angew. Chem. Int. Ed.2014, 53, 10759.
(b)Yang Y.; Mustard T. J. L.; Cheong P. H.-Y.; Buchwald, S. L. Angew. Chem. Int. Ed.2013, 52, 14098.
(c) Obora, Y.; Tsuji, Y.; Kobayashi, M.; Kawamura, T. J. Org. Chem. 1995, 60, 4647.
[6] (a) Wu H. B.; Ma X. T.; Tian S.-K. Chem. Commun.2014, 50, 219.
(b) Yang B.; Wang, Z. X. J. Org. Chem.2017, 82, 4542.
(c) Butt, N. A.; Zhang, W. Chem. Soc. Rev. 2015, 44, 7929.
(d) Gosmini, C.; Bégouin J. M.; Moncomble, A. Chem. Commun., 2008, 3221.
[7] (a) Wang S.; Qian Q.; Gong H. Org. Lett.2012, 14, 3352.
(b)Anka-Lufford, L. L.; Prinsell, M. R.; Weix, D. J. J. Org. Chem. 2012, 77, 9989.
(c) Gomes P.; Gosmini, C. Périchon, J. J. Org. Chem.2003, 68, 1142.
[8] (a) Everson D. A.; Shrestha R.; Weix, D. J. J. Am. Chem. Soc.2010, 132, 920.
(b) Han G. Y.; Su P.F.; Pan Q. Q.; Liu X. Y.; Shu, X. Z. Nat. Catal.2024, 7, 12.
(c) Kim, S.; Goldfogel, M. J.; Ahern, B. N.; Salgueiro, D. C.; Guzei, I. A.; Weix, D. J. J. Am. Chem. Soc., 2025, 147, 2616.
(d) Pang, X.; Su, P. F.; Shu, X. Z. Acc. Chem. Res. 2022, 55, 17, 2491-2509.
[9] (a) Zhao Z. Z.; Guo P.; Pang X.; Shu, X. Z. Acc. Chem. Res.2024, 57, 3356.
(b) Ehehalt L. E.; Beleh O. M.; Priest I. C.; Mouat J. M.; Olszewski A. K.; Ahern B. N.; Cruz A. R.; Chi B. K.; Castro A. J.; Kang K.; Wang J.; Weix, D. J. Chem. Rev.2024, 124, 13397.
[10] (a) Goebel J. F.; Löffler J.; Zeng Z.; Handelmann J.; Hermann A.; Rodstein I.; Gensch T.; Gessner V. H.; Gooßen, L. J. Angew. Chem. Int. Ed.2023, 62, e202216160.
(b) Chen D.; Lepori C.; Guillot R.; Gil R.; Bezzenine S.; Hannedouche, J. Angew. Chem. Int. Ed.2024, 63, e202408419.
(c)Mills, L. R. Organometallics 2025, 44, 858.
[11] (a) Chen H.; Jia X.; Yu Y.; Qian Q.; Gong, H. Angew. Chem., Chem. Int.2017, 56, 13103.
(b) Yan X. B.; Li C. L.; Jin W. J.; Guo P.; Shu, X. Z. Chem. Sci.2018, 9, 4529.
(c) Chen, R.; Intermaggio, N. E.; Xie, J.; Rossi-Ashton, J. A.; Gould, C. A.; Martin, R. T.; MacMillan, D. W. C. Science, 2024, 383, 1350.
(d) Lyon, W. L.; Wang, J. Z.; Alcázar, J.; MacMillan, D.W.C. J. Am. Chem. Soc. 2025, 147, 2296.
[12] (a) Huang Z.; Yu, Z. X. J. Am. Chem. Soc.2026, 148, 2, 2437.
(b) Ackerman L. K. G.; Lovell M. M.; Weix, D. J. Nature 2015, 524, 454.
(c) Olivares, A. M.; Weix, D. J. J. Am. Chem. Soc. 2018, 140, 2446.
[13] (a) He R. D.; Bai Y.; Han G. Y.; Zhao Z. Z.; Pang X.; Pan X.; Liu X. Y.; andShu, X. Z. Angew. Chem. Int. Ed.2022, 61, e202114556.
(b) Dworkin J. H.; Chen Z. M.; Cheasty K. C.; Rubio A. V.; Kwon, O. J. Am. Chem. Soc.2025, 147, 13531.
(c) Wu, T.; Castro, A. J.; Ganguli, K.; Rotella, M. E.; Ye, N.; Gallou, F.; Wu, B.; Weix, D. J. J. Am. Chem. Soc. 2025, 147, 9449.
(d) Liao, Z.; Li, Z.; Xiao, M.; Deng, Y.; Ma, Z.; Zhou, L.; Dai, G.; Li, X.; Wang, S.; Chen, S.; Li, J.; Tang, S. Nat Commun. 2025, 16, 7218.
(e) Tang, S.; Xu, Z. H.; Liu, T.; Wang, S. W.; Yu, J.; Liu, J.; Hong, Y.; Chen, S. L.; He, J.; Li, J. H. Angew. Chem. Int. Ed. 2021, 60, 21360-21367.
[14] Jia X. G.; Guo P.; Duan J.; Shu X. Z.Chem. Sci. 2018, 9, 640.
[15] (a) Peng M.; Zhang Y.; Wang X.;Gao H.; Tan B. Chem-asian J.2025, 20, e202401463.
(b) Gao R. R.; Chen C.; Huang Y. B.; Wang, X. Y. Angew. Chem., Int. Ed.2025, 64, e202500006.
(c) Liu, Y.; Deng, C.; Tang, L.; Qin, A; Hu, R.; Sun, J. Z.; Tang, B. Z. J. Am. Chem. Soc. 2011, 133, 660.
[16] (a) Li, W.; Chen, Y.; Yuan R.; Jia X.; Yao Y.; Zhang, L. Angew. Chem. Int. Ed.2025, 64, e202500315.
(b) Liu S.; Lu Y.; Wang H.; Xue Z.; Xu Z.; Wan H.; Yin Q.; Lv T.; Liu S. X.; Jin Y. ACS Catal.2025, 15, 4, 3306.
[17] Xu G. L.; Liu C. Y.; Pang, X; Liu, X. Y.; Shu, X. Z. CCS. Chem.2022, 4, 864.
[18] (a)Minami Y.; Yoshiyasu H.; Nakao Y.; Hiyama, T. Angew. Chem., Int. Ed.,2013, 52, 883
(b) Li Y.-X.; Xuan Q.-Q.; Liu L.; Wang D.; Chen Y.-J.; Li, C.-J. J. Am. Chem. Soc.,2013, 135, 12536.
(c) Miyazaki, Y.; Ohta, N.; Semba, K.; Nakao, Y. J. Am. Chem. Soc., 2014, 136, 3732.
[19] Farmer J. L.; Hunter H. N.; Organ M. G. J. Am. Chem. Soc.2012, 134, 17470.
[20] Yang Y.;Buchwald, S. L. J. Am. Chem. Soc.2013, 135, 29, 10642.
[21] (a) Farajidizaji B.; Thakellapalli H.; Akhmedov N. G.; Wang, K. K. J. Org. Chem.2018, 83, 1216.
(b) Gao C.; Prasad S. K. K.; Zhang B.; Dvořák M.; Tayebjee M. J. Y.; McCamey D. R.; Schmidt T. W.; Smith T. A.; Wong, W. W. H. J. Phys. Chem. C2019, 123, 20181.
(c)Fu, W.; Zhong, J.; Lv, S.; Song, X.; Xinga, Y.; Wang, Z.Org. Chem. Front., 2026,13, 1667.
[22] Alfaro R.; Parra A.; Alemán J.; Tortosa, M. J. Am. Chem. Soc.,2012, 134, 15165.

镍催化芳基/烯丙基交叉亲电偶联反应制备烯丙基取代芳基硼酸酯

Nickel-Catalyzed Aryl-Allyl Cross-Electrophile Coupling for the Synthesis of Allyl-Substituted Aryl Boronates

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