1,1'-亚甲基二咪唑鎓多氢键供体催化剂促进常压下CO2与环氧化物的环加成反应

doi:10.6023/cjoc202406041

摘要/Abstract

对新型氢键供体(HBD)催化剂的追求导致了其在有机合成领域的重大进展. 考虑到咪唑阳离子的吸电子强度和氢键给体的空间要求, 通过亚甲基桥接两个咪唑阳离子, 发展了一种基于1,1'-亚甲基二咪唑鎓支架的新型HBD催化剂. 这些催化剂在CO₂与环氧化物的环加成反应中表现出优异的性能, 在温和的条件下(常压, 80 ℃, 12 h, 1 mol%催化剂)获得了高达99%的产率和99%的选择性. 通过¹H NMR研究和密度泛函理论(DFT)计算, 详细研究了催化剂的几何结构、原子电荷分布和多HBD协同效应. 研究结果表明, 咪唑鎓环上C2-H、C2'-H、C5-H、C5'-H位置的质子以及桥接的亚甲基上的质子, 有助于形成具有适当距离和协同效应的多重氢键作用, 这对活化二氧化碳和环氧化物至关重要. 本研究突出了1,1'-亚甲基二咪唑鎓催化剂的独特特性, 并为开发高效多重HBD催化剂提供了宝贵的经验.

关键词: 1,1'-亚甲基二咪唑鎓, 多氢键供体催化剂, CO₂的环加成, 协同效应, 密度泛函理论(DFT)计算

The quest for innovative hydrogen-bond donor (HBD) catalysts has led to a significant advancement in the field of organic synthesis. Considering the electron-withdrawing strength of imidazolium cations and the spatial requirements of hydrogen bond donors, a novel HBD catalyst based on the 1,1'-methylenediimidazolium scaffold by bridging two imidazolium cations with methylene was developed. The 1,1'-methylenediimidazolium-based catalysts exhibit excellent performance in the cycloaddition reaction of CO₂ and epoxides, achieving up to 99% yield and 99% selectivity under mild conditions (atmospheric pressure, 80 ℃ for 12 h, with 1 mol% catalyst). The geometric structure, atomic charge distribution, and synergistic effect of HBD catalysts were studied in detail through ¹H NMR spectroscopy and density functional theory (DFT) calculations. The research results indicate that the protons at positions C2-H, C2'-H, C5-H, and C5'-H on the imidazolium rings, as well as the protons on the bridged methylene, contribute to the formation of multiple hydrogen bonds with appropriate distance and synergistic effects, which are crucial for activating CO₂ and epoxides. This research highlights the distinctive attributes of 1,1'-methylenediimidazolium-based catalysts and offers valuable insights into the development of highly efficient multiple HBD catalysts.

Key words: 1,1'-methylenediimidazolium, multiple hydrogen-bond donor catalysts, cycloaddition of CO₂, cooperative effects, density functional theory (DFT) calculation

引用此文

陈学伟, 于方彩, 田传洪. 1,1'-亚甲基二咪唑鎓多氢键供体催化剂促进常压下CO₂与环氧化物的环加成反应[J]. 有机化学, 2024, 44(10): 3198-3205.

Xuewei Chen, Fangcai Yu, Chuanhong Tian. 1,1'-Methylenediimidazolium-Based Multiple Hydrogen-Bond Donor Catalysts Facilitate the Cycloaddition of CO₂ with Epoxides under Atmospheric Pressure[J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3198-3205.

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

分享此文

图/表 8

Figure 1. Catalysts investigated in the paper

Figure 2. Hydrogen-bond interactions investigated by 1H NMR method

Entry	Catalysts	Yield^b/%	Selectivity^b/%
1	EMImBr	70	99
2^c	EMImBr	73	99
3	BMImBr	77	99
4	(MIm)₂MBr₂	25	99
5	(EIm)₂MBr₂	77	99
6	(BIm)₂MBr₂	83	99
7	(EIm)₂EBr₂	73	99
8	(BIm)₂MCl₂	31	99
9	Diphenylthiourea	5	99

Table 1. Optimization of catalysts in the cycloaddition reaction of CO2 with ECHa

Entry	(BIm)₂MBr₂/mol%	T/℃	t/h	Yield/%
1	1.0	80	12	99
2	1.0	70	12	91
3	1.0	60	12	83
4	1.0	50	12	67
5	0.5	80	12	92
6	0.1	80	12	78
7	1.0	80	10	96
8	1.0	80	8	89
9	1.0	80	6	75
10	1.0 cat.+2.5 H₂O	80	12	70

Table 2. Optimization of reaction conditionsa

Entry	Epoxide	Carbonate	Yield/%
1			93
2			91
3			90
4			89

Table 3. Substrate generality investigation catalyzed by (BIm)2- MBr2a

Reuse	Yield/%	Selectivity/%
1st	99	99
2nd	98	99
3rd	98	99
4th	97	99
5th	96	99

Table 4. Reuse of (BIm)2MBr2a

Figure 3. Notional model structures of (BIm)2MBr2, (BIm)2MBr2-ECH adduct and (BIm)2MBr2-ECH-CO2 adduct in DMSO solution optimized by DFT calculation at B3LYP/6-311++g(d, p) level of theory (a) Hydrogen-bond donors distances; (b) the location of bromide in (BIm)2MBr2. Hydrogen-bond interactions in (BIm)2MBr2-ECH adduct (c) and (BIm)2- MBr2-ECH-CO2 adduct (d). Hydrogen, carbon, oxygen, nitrogen, bromide and chlorine atoms are shown in white, gray, red, blue, brown and green.

Scheme 1. Elementary mechanism for cycloaddition reaction prompted by (BIm)2MBr2

参考文献 48

[1]	Huang, Y.; Unni, A. K.; Thadani, A. N.; Rawal, V. H. Nature 2003, 424, 146.
[2]	Taylor, M. S.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2006, 45, 1520.
[3]	Doyle, A. G.; Jacobsen, E. N. Chem. Rev. 2007, 107, 5713.
[4]	Pihko, P. M. Hydrogen Bonding in Organic Synthesis, Wiley-VCH, Weinheim, 2009.
[5]	Banik, S. M.; Levina, A.; Hyde, A. M.; Jacobsen, E. N. Science 2017, 358, 761.
[6]	Taylor, M. S.; Tokunaga, N.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 6700.
[7]	Wang, C.; Dong, X.; Zhang, Z.; Xue, Z.; Teng, H. J. Am. Chem. Soc. 2008, 130, 8606.
[8]	Malerich, J. P.; Hagihara, K.; Rawal, V. H. J. Am. Chem. Soc. 2008, 130, 14416.
[9]	Beletskiy, E. V.; Schmidt, J.; Wang, X. B.; Kass, S. R. J. Am. Chem. Soc. 2012, 134, 18534. doi: 10.1021/ja3085862 pmid: 23113730
[10]	Gotico, P.; Boitrel, B.; Guillot, R.; Sircoglou, M.; Quaranta, A.; Halime, Z.; Leibl, W.; Aukauloo, A. Angew. Chem., Int. Ed. 2019, 58, 4504.
[11]	Wu, R.; Chang, X.; Lu, A.; Wang, Y.; Wu, G.; Song, H.; Zhou, Z.; Tang, C. Chem. Commun. 2011, 47, 5034.
[12]	Chen, X.; Xin, Y.; Liu, Q.; Lan, Z. Chin. J. Org. Chem. 2016, 36, 306. (in Chinese)
	(陈学伟, 辛玉娟, 刘青, 兰支利, 有机化学, 2016, 36, 306.) doi: 10.6023/cjoc201508029
[13]	Samet, M.; Buhle, J.; Zhou, Y. W.; Kass, S. R. J. Am. Chem. Soc. 2015, 137, 4678.
[14]	Fan, Y.; Kass, S. R. Org. Lett. 2016, 18, 188.
[15]	Guan, R.; Zhang, X.; Chang, F.; Xue, N.; Yang, H. Chin. J. Catal. 2019, 40, 1874.
[16]	Park, Y.; Harper, K. C.; Kuhl, N.; Kwan, E. E.; Liu, R. Y.; Jacobsen, E. N. Science 2017, 355, 162.
[17]	Kaneko, S.; Kumatabara, Y.; Shimizu, S.; Maruoka, K.; Shirakawa, S. Chem. Commun. 2017, 53, 119.
[18]	Sakakura, T.; Choi, J. C.; Yasuda, H. Chem. Rev. 2007, 107, 2365.
[19]	Aresta, M.; Dibenedetto, A.; Angelini, A. Chem. Rev. 2014, 114, 1709.
[20]	Kamphuis, A. J.; Picchioni, F.; Pescarmona, P. P. Green Chem. 2019, 21, 406. doi: 10.1039/c8gc03086c
[21]	Comerford, J. W.; Ingram, I. D. V.; North, M.; Wu, X. Green Chem. 2015, 17, 1966.
[22]	Liu, G.; Fu, Z.; Chen, F.; Xu, C.; Li, M.; Liu, N. Chin. J. Org. Chem. 2023, 43, 629. (in Chinese)
	(刘桂杰, 付正强, 陈飞, 徐彩霞, 李敏, 刘宁, 有机化学, 2023, 43, 629.) doi: 10.6023/cjoc202206047
[23]	Cokoja, M.; Wilhelm, M. E.; Anthofer, M. H.; Herrmann, W. A.; Kühn, F. E. ChemSusChem 2015, 8, 2436. doi: 10.1002/cssc.201500161 pmid: 26119776
[24]	Kessaratikoon, T.; Theerathanagorn, T.; Crespy, D.; D'Elia, V. J. Org. Chem. 2023, 88, 4894.
[25]	Li, Z.; Zhang, Y.; Zheng, Y.; Li, B.; Wu, G. J. Org. Chem. 2022, 87, 3145.
[26]	Peng, J.; Deng, Y. New J. Chem. 2001, 25, 639.
[27]	Li, Y.; Dominelli, B.; Reich, R. M.; Liu, B.; Kühn, F. E. Catal. Commun. 2019, 124, 118.
[28]	Bezerra, W. D. A.; Milani, J. L. S.; Franco, C. H. D. J.; Martins, F. T.; Fatima, A. D.; Mata, A. F. A. D.; Chagas, P. D. Mol. Catal. 2022, 530, 112632.
[29]	Han, G.; Xu, M.; Fan, H.; Guo, Q.; Guo, M.; Li, F. Catal. Commun. 2023, 106592.
[30]	Wulf, A.; Fumino, K.; Ludwig, R. Angew. Chem., Int. Ed. 2010, 49, 449.
[31]	Quezada, C. A.; Garrison, J. C.; Tessier, C. A.; Youngs, W. J. J. Organomet. Chem. 2003, 671, 183.
[32]	Lee, C. S.; Pal, S.; Yang, W. S.; Hwang, W. S.; Lin, I. J. B. J. Mol. Catal. A: Chem. 2008, 280, 115.
[33]	Crowhurst, L.; Mawdsley, P. R.; Perez-Arlandis, J. M.; Salter, P. A.; Welton, T. Phys. Chem. Chem. Phys. 2003, 5, 2790.
[34]	Fei, Z.; Zhao, D.; Geldbach, T. J.; Scopelliti, R.; Dyson, P. J. Chem. Eur. J. 2004, 10, 4886.
[35]	Chen, X. Ph.D. Dissertation, Hunan University, Changsha, 2008. (in Chinese)
	(陈学伟, 博士论文, 湖南大学, 长沙, 2008.)
[36]	Friebolin, H. Basic One- and Two-Dimensional NMR Spectroscopy, 4th ed., Wiley-VCH, Weinheim, 2008.
[37]	Ema, T.; Miyazaki, Y.; Shimonishi, J.; Maeda, C.; Hasegawa, J. Y. J. Am. Chem. Soc. 2014, 136, 15270.
[38]	Sun, J.; Ren, J.; Zhang, S.; Cheng, W. Tetrahedron Lett. 2009, 50, 423.
[39]	Bobbink, F. D.; Vasilyev, D.; Hulla, M.; Chamam, S.; Menoud, F.; Laurenczy, G.; Katsyuba, S.; Dyson, P. J. ACS Catal. 2018, 8, 2589.
[40]	Legault, C. Y. CYLview, 1.0b, Université de Sherbrooke: Québec, Canada, 2009, http://www.cylview.org.
[41]	Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
[42]	Murray, J. S.; Politzer, P. WIREs Comput. Mol. Sci. 2011, 1, 153.
[43]	Liu, J.; Wei, X.; Wei, Z.; Liu, J.; Zheng, L. Acta Crystallogr. 2009, E65, o2027.
[44]	Peppel, T.; Spannenberg, A. IUCrData 2018, 3, x181212.
[45]	Peng, Q.; Paton, R. S. Acc. Chem. Res. 2016, 49, 1042.
[46]	North, M.; Pasquale, R. Angew. Chem., Int. Ed. 2009, 48, 2946.
[47]	Bhunia, S.; Molla, R. A.; Kumari, V.; Islam, S. M.; Bhaumik, A. Chem. Commun. 2015, 51, 15732.
[48]	Chen, J.; Wu, X.; Ding, H.; Liu, N.; Liu, B.; He, L. ACS Sustainable Chem. Eng. 2021, 9, 16210.

1,1'-亚甲基二咪唑鎓多氢键供体催化剂促进常压下CO₂与环氧化物的环加成反应

1,1'-Methylenediimidazolium-Based Multiple Hydrogen-Bond Donor Catalysts Facilitate the Cycloaddition of CO₂ with Epoxides under Atmospheric Pressure

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 8

参考文献 48

相关文章 10

编辑推荐

相关统计

本文评价

[1]	刘婷婷, 胡宇才, 沈安. 亚胺配体协同氮杂环卡宾钯配合物催化碳碳偶联反应的作用机制[J]. 有机化学, 2023, 43(2): 622-628.
[2]	胥稳智, 李雪, 韩孟楠, 周婷婷, 杨瑜涛, 李玮. 一种基于协同效应的肼荧光探针及其在细胞成像中的应用[J]. 有机化学, 2020, 40(1): 181-185.
[3]	李英俊, 赵月, 靳焜, 高立信, 盛丽, 刘雪洁, 杨鸿境, 林乐弟, 李佳. 含咔唑/苯并咪唑环的2,5-二取代-1,3,4-噻二唑酰胺衍生物的合成及对PTP1B/TCPTP抑制活性的评价[J]. 有机化学, 2019, 39(9): 2599-2608.
[4]	王超, 邓楠, 王玲玲, 许定健, 姚小泉. 铜-银双金属纳米颗粒催化的醛-端炔加成反应研究[J]. 有机化学, 2016, 36(5): 1034-1043.
[5]	张利利,刘安华,曾幸荣. 双环笼状取代倍半硅氧烷的合成与表征[J]. 有机化学, 2007, 27(03): 424-427.
[6]	刘流,张海涛,王云普. 水溶性高负责担载二茂铁希夫碱与DNA的作用[J]. 有机化学, 2003, 23(6): 570-573.
[7]	钟毅,尤启冬. 双中心协同催化作用在不对称合成中的应用[J]. 有机化学, 2002, 22(7): 453-461.
[8]	廖德仲,何节玉. 新型固体酸SO^2^-~4-MoO3-TiO2催化合成丙酸正丁酯的研究[J]. 有机化学, 2001, 21(12): 1153-1156.
[9]	刘中立. 生物抗氧化剂作用的微环境效应和协同效应[J]. 有机化学, 2001, 21(11): 884-889.
[10]	杨炳辉,姜纪清. 碳糖苷合成的新进展[J]. 有机化学, 1998, 18(4): 303-310.