端炔偶联反应中铜变价催化机制的理论研究

doi:10.6023/cjoc202112041

有机化学 ›› 2022, Vol. 42 ›› Issue (6): 1811-1819.DOI: 10.6023/cjoc202112041 上一篇下一篇

研究论文

端炔偶联反应中铜变价催化机制的理论研究

马丽文, 魏晓叶, 赵紫琳, 赵昂, 邓祥文, 霍丙南, 马刚, 张春芳^*()

河北大学化学与环境科学学院河北保定 071002

收稿日期:2021-12-30 修回日期:2022-01-25 发布日期:2022-02-17
通讯作者: 张春芳
基金资助:
国家自然科学基金(11704024); 国家自然科学基金(21973024); 河北省自然科学基金(B2020201006); 河北大学人才引进项目(521000981133); 河北大学在读研究生创新能力培养(HBU2021ss021); 河北大学2021年课程思政教学改革研究(KCSZ21053); 河北大学第三批“精品实验项目”(2021-BZ-JPSY37); 河北大学大学生创新创业训练计划项目(2020281); 河北大学大学生创新创业训练计划项目(2021184); 河北大学化学与环境科学学院第二批本科教学改革(H2-04004); 河北大学化学与环境科学学院第二批本科教学改革(H2-06001)

Theoretical Study on the Catalytic Mechanism of Copper with Various Valence for the Terminal Alkyne Coupling Reaction

Liwen Ma, Xiaoye Wei, Zilin Zhao, Ang Zhao, Xiangwen Deng, Bingnan Huo, Gang Ma, Chunfang Zhang()

College of Chemistry & Environmental Science, Hebei University, Baoding, Hebei 071002

Received:2021-12-30 Revised:2022-01-25 Published:2022-02-17
Contact: Chunfang Zhang
Supported by:
National Natural Science Foundation of China(11704024); National Natural Science Foundation of China(21973024); Natural Science Foundation of Hebei Province(B2020201006); Advanced Talents Incubation Program of the Hebei University(521000981133); Post-Graduate's Innovation Fund Project of Hebei University(HBU2021ss021); 2021 Curriculum Ideological and Political Education of Hebei University(KCSZ21053); Third Excellent Experimental Project of Hebei University(2021-BZ-JPSY37); College Studentsʼ Innovation and Entrepreneurship Training Program of Hebei University(2020281); College Studentsʼ Innovation and Entrepreneurship Training Program of Hebei University(2021184); Teaching and Reform Project of College of Chemistry & Environmental Science, Hebei University(H2-04004); Teaching and Reform Project of College of Chemistry & Environmental Science, Hebei University(H2-06001)

文章分享

1. 221811S.pdf(1299KB)

摘要/Abstract

铜催化端炔对称偶联是合成共轭二炔的重要反应. 基于密度泛函理论和Marcus公式, 研究了苯乙炔(Phenylacetylene, PAY)对称偶联的铜变价催化机制. 结果表明, 在有机溶剂中PAY优先与一价铜络合物配位, 并经单电子转移变为二价铜络合的端炔1. 端炔1经质子消除生成一价铜炔化物2. 2与PAY加成为铜炔化物3. 3经分子内H转移、C_sp—C_sp偶联、配体交换生成1,4-二苯基丁二炔(1,4-Diphenyl-1,3-butadiyne, DPBY); 或3经分子间质子消除、 C_sp—C_sp偶联、单电子转移以及配体交换反应生成DPBY. 此外, 强碱条件下易生成PAY^–, PAY^–与2加成为铜炔化物3', 3'经歧化反应(单重态和三重态势能面交叉)生成铜炔化物14, 14解离得到DPBY. 电荷分析表明, 上述反应过程存在一价和零价中间体以及过渡态, 解释了文献中测得多种不同价态铜络合物的原因.

关键词: 铜变价催化, 端炔对称偶联, 单电子转移, 氧化还原电势, 密度泛函理论计算

Copper-catalyzed homo-coupling reaction of terminal alkynes is of significant importance for the synthesis of conjugated diynes. Based on density functional theory and Marcus formula, the reaction mechanism for the copper-catalyzed homo-coupling reaction of phenylacetylene (PAY) is reported. Our calculations show that PAY is preferentially coordinated with the cuprous complexes in different organic solvents, which is transferred to Cu(II)-acetylide (complex 1) by single electron transfer reaction. Complex 1 is subsequently transferred to Cu(I)-acetylide (complex 2) by proton elimination reaction. Another PAY is added to complex 2 forming complex 3, of which the terminal H is transferred intramolecularly. Followed by C_sp—C_sp coupling and ligand exchange reactions, 1,4-diphenyl-1,3-butadiyne (DPBY) is obtained. Besides, the complex 3 could also become DPBY via subsequent intermolecular proton elimination, C_sp—C_sp coupling, SET and ligand exchange reactions. In addition, under the strong base condition, phenylacetylene anion (PAY^–) is generated and then add to complex 2 forming complex 3'. Complex 3' then changes into complex 14 through disproportionation reaction, where the singlet-triplet coupling is involved. Complex 14 is dissociated into DPBY directly. The charges are computed for all the involved complexes, which are Cu(0)/(I) intermediates and Cu(II)/(I) transition states, illustrating the observed copper species with different valence in experiments.

Key words: Cu-catalysis with variable valence, homo-coupling of terminal alkyne, single electron transfer, redox potential, density functional theory

引用此文

马丽文, 魏晓叶, 赵紫琳, 赵昂, 邓祥文, 霍丙南, 马刚, 张春芳. 端炔偶联反应中铜变价催化机制的理论研究[J]. 有机化学, 2022, 42(6): 1811-1819.

Liwen Ma, Xiaoye Wei, Zilin Zhao, Ang Zhao, Xiangwen Deng, Bingnan Huo, Gang Ma, Chunfang Zhang. Theoretical Study on the Catalytic Mechanism of Copper with Various Valence for the Terminal Alkyne Coupling Reaction[J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1811-1819.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图式1. TMEDA-Cu-PAY络合物的形成

Scheme 1. Formation mechanism of TMEDA-Cu-PAY complex The subscript o of ΔG is the corresponding to the o-dichlorobenzene corrected free energies, p to pyridine, a to acetone, and t to trichloromethane

图式2. PAY在不同碱中的氢消除反应

Scheme 2. Hydrogen elimination reaction of PAY in different bases The subscript o of ΔG is the corresponding to the o-dichlorobenzene corrected free energies, p to pyridine, a to acetone, and t to trichloromethane

图1. 不同价态铜络合物的氢消除反应和SET过程

Figure 1. Dehydrogenation reactions and SET of various copper complexes with different valence The values below are the free energies in o-dichlorobenzene, pyridine, acetone and trichloromethane solvents, respectively; the values in brackets are the free energies taken O2 as oxidant

Species	E_RED/V
Species	ODCB	Py	AC	CHCl₃
[TMEDA-Cu(I)-PAY]⁺	0.095	0.092	0.089	0.11
TMEDA-Cu(I)-dehydro-PAY	–0.028	–0.023	–0.018	–0.048
[TMEDA-Cu(II)-PAY]²⁺	0.90	0.90	0.89	0.94
[TMEDA-Cu(II)-dehydro-PAY]⁺	0.53	0.53	0.53	0.55

表1. 不同物质的还原电势ERED

Table 1. Reduction potentials ERED of different species

图2. 二价铜络合物涉及分子间氢转移的Csp—Csp偶联反应二价铜络合物涉及分子间氢转移的Csp—Csp偶联反应

Figure 2. Csp—Csp coupling mechanism of divalent copper complex involving intramolecular hydrogen transfer Lines and values in Black, Red, Blue and Green are corresponding to the solvent corrected free energy by o-dichlorobenzene, pyridine, acetone and trichloromethane, respectively

图3. 二价铜络合物涉及SET的Csp—Csp偶联反应

Figure 3. Csp—Csp coupling mechanism of divalent copper complex involving the SET procedure Lines and values in Black, Red, Blue and Green are corresponding to the solvent corrected free energy by o-dichlorobenzene, pyridine, acetone and trichloromethane, respectively

图4. 二价铜络合物涉及歧化反应的Csp—Csp偶联反应机制

Figure 4. Csp—Csp coupling mechanism of divalent copper complex involving disproportionation reaction Lines and values in Black, Red, Blue and Green are corresponding to the solvent corrected free energy by o-dichlorobenzene, pyridine, acetone and trichloromethane, respectively

参考文献 38

[1]	Roh, S. W.; Choi, K.; Lee, C. Chem. Rev. 2019, 119, 4293. doi: 10.1021/acs.chemrev.8b00568
[2]	Li, Y. J.; Xu, L.; Liu, H. B.; Li, Y. L. Chem. Soc. Rev. 2014, 43, 2572. doi: 10.1039/c3cs60388a
[3]	He, J. J.; Wang, N.; Cui, Z. L.; Du, H. P.; Fu, L.; Huang, C. S.; Yang, Z.; Shen, X. Y.; Yi, Y. P.; Tu, .Z. Y.; Li, Y. L. Nat. Commun. 2017, 8, 1172. doi: 10.1038/s41467-017-01202-2
[4]	Yu, J. M.; Liu, L.; Xu, B. M.; Liu, Z. Y; Shan, S. X. Acta Chim. Sinica 1996, 54, 922. (in Chinese)
	( 余俊梅, 刘林, 徐保明, 刘智勇, 单书香, 化学学报, 1996, 54, 922.)
[5]	Ma, N.; Zeng, X. H. Chin. J. Org. Chem. 2018, 38, 1556. (in Chinese) doi: 10.6023/cjoc201712038
	( 马楠, 曾祥华, 有机化学, 2018, 38, 1556.) doi: 10.6023/cjoc201712038
[6]	Zhang, C. X.; Li, N. N.; Li, X.; Chang, H. H.; Liu, Q.; Wei, W. L. Chin. J. Org. Chem. 2014, 34, 81. (in Chinese) doi: 10.6023/cjoc201307024
	( 张聪霞, 李娜娜, 李兴, 常宏宏, 刘强, 魏文珑, 有机化学, 2014, 34, 81.) doi: 10.6023/cjoc201307024
[7]	Sun, S. J.; Bao, Y. S.; Zhaori, G. T. J. Mol. Catal. 2013, 27, 585. (in Chinese)
	( 孙淑君, 包永胜, 照日格图, 分子催化, 2013, 27, 585.)
[8]	Zhang, M.; Wang, L. L.; Li, L. C.; Tian, A. M. Chin. J. Org. Chem. 2013, 33, 2169. (in Chinese) doi: 10.6023/cjoc201303011
	( 张明, 王玲玲, 李来才, 田安明, 有机化学, 2013, 33, 2169.) doi: 10.6023/cjoc201303011
[9]	Bai, D. H.; Li, C. L.; Li, J.; Jia, X. S. Chin. J. Org. Chem. 2012, 32, 994. (in Chinese) doi: 10.6023/cjoc1202073
	( 白东虎, 李春举, 李健, 贾学顺, 有机化学, 2012, 32, 994.) doi: 10.6023/cjoc1202073
[10]	Hay, A. S. J. Org. Chem. 1962, 27, 3320. doi: 10.1021/jo01056a511
[11]	Evano, G.; Blanchard, N. Copper-Mediated Cross-Coupling Reactions, John Wiley & Sons, Inc., Hoboken, New Jersey, Published simultaneously in Canada, 2013.
[12]	Karlin, K. D.; Itoh, S. Copper-Oxygen Chemistry, John Wiley & Sons, Inc., Hoboken, New Jersey, Published simultaneously in Canada, 2011.
[13]	Su, L. B.; Dong, J. Y.; Liu, L.; Sun, M. L.; Qiu, R. H.; Zhou, Y. B.; Yin, S. F. J. Am. Chem. Soc. 2016, 138, 12348. doi: 10.1021/jacs.6b07984
[14]	Zhang, Z. H.; Dong, X. Y.; Du, X. Y.; Gu, Q. S.; Li, Z. L.; Liu, X. Y. Nat. Commun. 2019, 10, 5689. doi: 10.1038/s41467-019-13705-1
[15]	Siemsen, P.; Livingston, R. C.; Diederich, F. Angew. Chem., Int. Ed. 2000, 39, 2632. doi: 10.1002/1521-3773(20000804)39:15【-逻辑与-】#x00026;lt;2632::AID-ANIE2632【-逻辑与-】#x00026;gt;3.0.CO;2-F
[16]	Bohlmann, F.; Schnowsky, H.; Inhoffen, E.; Grau, G.; Chem. Ber. 1964, 97, 794. doi: 10.1002/cber.19640970322
[17]	Seavill, P. W.; Holt, K. B.; Wilden, J. D. Faraday Discuss. 2019, 220, 269. doi: 10.1039/c9fd00031c pmid: 31502612
[18]	Jiang, H. F.; Tang, J. Y.; Wang, A. Z.; Deng, G. H.; Yang, S. R. Synthesis 2006, 7, 1155.
[19]	Fomina, L.; Vazquez, B.; Tkatchouk, E.; Fomine, S. Tetrahedron 2002, 58, 6741. doi: 10.1016/S0040-4020(02)00669-5
[20]	Bakhoda, A.; Okoromoba, O. E.; Greene, C.; Boroujeni, M. R.; Bertke, J. A.; Warren, T. H. J. Am. Chem. Soc. 2020, 142, 18483. doi: 10.1021/jacs.0c07137
[21]	Bai, R. P.; Zhang, G. G.; Yi, H.; Huang, Z. L.; Qi, X.T.; Liu, C.; Miller, J. T.; Kropf, A. J.; Bunel, E. E.; Lan, Y.; Lei, A.W. J. Am. Chem. Soc. 2014, 136, 16760. doi: 10.1021/ja5097489
[22]	Houmam, A. Chem. Rev. 2008, 108, 2180.
[23]	Wu, L. M.; Guo, X.; Wang, J.; Guo, Q. X.; Liu, Z. L.; Liu, Y. C. Sci. China, Ser. B Chem. 1998, 27, 540. (in Chinese)
	( 吴隆民, 郭霞, 王隽, 郭庆祥, 刘中立, 刘有成, 中国科学(B辑), 1998, 27, 540.)
[24]	Luo, S.; Wei, Z. S.; Dionysiou, D. D.; Spinney, R.; Hu, W. P.; Chai, L. Y.; Ye, T. T.; Xiao, R. Y. Chem. Eng. J. 2017, 327, 1056. doi: 10.1016/j.cej.2017.06.179
[25]	Wang, D.; Huang, S. P.; Wang, C.; Yue, Y.; Zhang, Q. S. Org. Electron. 2019, 64, 216. doi: 10.1016/j.orgel.2018.10.038
[26]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery Jr, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 09, Rev. B.01, Wallingford, CT, 2010.
[27]	Wang, G.; Bai, K. K.; Li, L. C.; Tian, A. M. Sci. China-Chem. 2014, 44, 334. (in Chinese)
	( 王刚, 白坤坤, 李来才, 田安民, 中国科学:化学, 2014, 44, 334.)
[28]	Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215. doi: 10.1007/s00214-007-0310-x
[29]	Wu, T. Z.; Kalugina, Y. N.; Thakkar, A. J. Chem. Phys. Lett. 2015, 635, 257. doi: 10.1016/j.cplett.2015.07.003
[30]	Alecu, I. M.; Zheng, J. J.; Zhao, Y.; Truhlar, D. G. J. Chem. Theory Comput. 2010, 6, 2872. doi: 10.1021/ct100326h pmid: 26616087
[31]	Man, Q. M.; Fu, Z. Y.; Liu, T. T.; Zheng, M. Y.; Jiang, H. L. Acta Chim. Sinica 2021, 79, 948. (in Chinese) doi: 10.6023/A21040172
	( 满清敏, 付尊蕴, 刘甜甜, 郑明月, 蒋华良, 化学学报 2021, 79, 948.) doi: 10.6023/A21040172
[32]	Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378. doi: 10.1021/jp810292n
[33]	Gao, Y. P.; Ji, Y. M.; Li, G. Y.; An, T. C. Water Res. 2014, 493, 60.
[34]	Luo, S.; Wei, Z. S.; Spinney, R.; Villamena, F. A.; Dionysiou, D. D.; Cheng, D.; Tang, C. J.; Chai, L. Y.; Xiao, R. Y. J. Hazard. Mater. 2018, 344, 1165. doi: 10.1016/j.jhazmat.2017.09.024
[35]	Xiao, R.; Noerpel, M.; Luk, H.L.; Wei, Z.S.; Spinney, R. Int. J. Quantum Chem. 2014, 114, 74. doi: 10.1002/qua.24518
[36]	Nelsen, S. F.; Weaver, M. N.; Luo, Y.; Pladziewicz, J. R.; Ausman, L. K.; Jentzsch, T. L; O’Konek, J. J. J. Phys. Chem. 2012, 110, 11665.
[37]	Ziegler, M.S.; Lakshmi, K.V.; Tilley, T. D. J. Am. Chem. Soc. 2017, 139, 5378. doi: 10.1021/jacs.6b13261 pmid: 28394586
[38]	Kundu, S.; Greene, C.; Williams, K. D.; Salvador, T. K.; Bertke, J. A.; Cundari, T. R.; Warren, T. H. J. Am. Chem. Soc. 2017, 139, 9112. doi: 10.1021/jacs.7b04046

端炔偶联反应中铜变价催化机制的理论研究

Theoretical Study on the Catalytic Mechanism of Copper with Various Valence for the Terminal Alkyne Coupling Reaction

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 7

参考文献 38

相关文章 15

编辑推荐

相关统计

本文评价

[1]	徐伟, 翟宏斌, 程斌, 汪太民. 可见光诱导的钯催化Heck反应[J]. 有机化学, 2023, 43(9): 3035-3054.
[2]	杨晓娜, 郭宏宇, 周荣. 可见光促进有机硅化合物参与的化学转化[J]. 有机化学, 2023, 43(8): 2720-2742.
[3]	宋戈洋, 薛东. 光促进过渡金属催化的C-杂原子键偶联反应进展[J]. 有机化学, 2022, 42(8): 2275-2299.
[4]	余卫国, 王灵娜, 俞晓聪, 罗书平. 荧光染料和镍协同催化的脱羧羰基化反应[J]. 有机化学, 2022, 42(4): 1216-1223.
[5]	徐曼, 夏远志. 铑(III)催化N-苯氧基乙酰胺与亚甲基氧杂环丁酮氧化还原中性的碳氢活化/环化反应的机理研究[J]. 有机化学, 2021, 41(8): 3272-3278.
[6]	黄利, 王毓浩, 刘吉英, 李世俊, 张文静, 蓝宇. 铜催化异氰酸酯加成反应机理研究[J]. 有机化学, 2021, 41(11): 4347-4352.
[7]	史敦发, 王露, 夏春谷, 刘超. 可见光促进烷基硼化合物转化研究进展[J]. 有机化学, 2020, 40(11): 3605-3619.
[8]	孔黎春, 周雨露, 罗芳, 朱钢国. 醛基为受体的氧化自由基加成反应研究进展[J]. 有机化学, 2018, 38(11): 2858-2865.
[9]	阮利衡, 董振诚, 陈春欣, 吴爽, 孙京. 过渡金属镍与可见光双催化体系的研究进展[J]. 有机化学, 2017, 37(10): 2544-2554.
[10]	王凇旸, 郭冠南, 杨东, 胡建华. Cu催化的单电子转移活性自由基聚合制备石墨烯/聚N,N-二甲基丙烯酰胺复合体系[J]. 有机化学, 2014, 34(7): 1382-1390.
[11]	董超, 谭广慧, 金英学. 基于光诱导单电子转移反应的三环异吲哚酮并环肽的合成[J]. 有机化学, 2014, 34(3): 578-583.
[12]	粱波颖, 金英学, 于沙沙, 曲凤玉, 谭广慧. 光诱导单电子转移反应合成硫杂、氮杂冠醚[J]. 有机化学, 2013, 33(9): 1950-1954.
[13]	蔡晓冰, 胡薇, 陆国林, 黄晓宇. PPEGMEA-g-PBLG两亲性接枝共聚物的合成及其作为阿霉素输送载体的研究[J]. 有机化学, 2013, 33(12): 2520-2527.
[14]	粱波颖, 金英学, 于沙沙, 曲凤玉, 谭广慧. 基于光诱导单电子转移反应历程合成醚-聚N-苄基甘氨酸肽环化物[J]. 有机化学, 2013, 33(08): 1762-1768.
[15]	金英学, 王欣, 曲凤玉, 谭广慧, 岳群峰. N-(末端三丁基锡取代基)酰亚胺的光诱导单电子转移成环反应[J]. 有机化学, 2012, 32(12): 2363-2367.