喹啉及其衍生物的多相不对称氢转移反应

doi:10.1016/S1872-2067(20)63764-0

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1576-1585.DOI: 10.1016/S1872-2067(20)63764-0

喹啉及其衍生物的多相不对称氢转移反应

任亦起^a^,^b, 陶琳^a^,^b, 李纯志^a^,^b, Sanjeevi Jayakumar^a, 李贺^a, 杨启华^a^,^*()

^a中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连116023
^b中国科学院大学, 北京100049

收稿日期:2020-12-18 接受日期:2021-01-18 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 杨启华
作者简介:^* 电话: (0411) 84379552; 传真: (0411)84694447; 电子信箱: yangqh@dicp.ac.cn
基金资助:
国家重点研发计划(2017YFB0702800);国家自然科学基金重点项目(21733009);国家自然科学基金重点项目(21972134);中国科学院战略性科技先导专项(XDB17020200)

Development of efficient solid chiral catalysts with designable linkage for asymmetric transfer hydrogenation of quinoline derivatives

Yiqi Ren^a^,^b, Lin Tao^a^,^b, Chunzhi Li^a^,^b, Sanjeevi Jayakumar^a, He Li^a, Qihua Yang^a^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-12-18 Accepted:2021-01-18 Online:2021-09-18 Published:2021-05-16
Contact: Qihua Yang
About author:^* Tel: +86-411-84379552; Fax: +86-411-84694447; E-mail: yangqh@dicp.ac.cn
Supported by:
National Key R&D Program of China(2017YFB0702800);National Natural Science Foundation of China(21733009);National Natural Science Foundation of China(21972134);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020200)

摘要/Abstract

摘要：

喹啉及其衍生物的多相不对称氢转移是制备杂环手性化合物的理想策略. 多相手性催化体系具有催化剂可循环利用及产物分离提纯容易等优势. 然而, 喹啉及其衍生物的多相手性高效催化体系鲜有报道. 这主要是由于多相手性氢转移为水-油-固三相反应, 在反应的过程中, 传质问题极大影响固体催化剂的催化性能. 因此, 发展具有相转移功能的手性催化材料, 是提高多相氢转移体系催化效率的有效途径.
本文采用一锅法合成策略, 通过离子液体(ILs)为连接基团实现了TsDPEN手性配体在SBA-15介孔孔道中的嫁接. 与Rh盐配位后, 获得手性固体催化剂SBA-ILBF₄-TsDPEN-Rh. FI-IR光谱和¹³C NMR结果表明, 手性催化活性中心成功负载在SBA-15中, 随着手性活性中心负载量的增加, SBA-ILBF₄-TsDPEN-Rh的比表面积、孔径和孔容逐渐降低. 在喹啉衍生物不对称氢转移反应中, SBA-ILBF₄-TsDPEN-Rh系列催化剂催化得到产物的ee值为91%, 表明多相手性催化剂具有较高的手性选择性. 多相手性催化剂的催化活性随着活性中心负载量的上升而呈现下降的趋势, 这主要是由于活性中心负载量较低的多相催化剂具有更高的比表面积和孔容, 更有利于催化过程中的传质. 与均相手性催化剂相比, 优化后的多相手性催化剂表现出更高的催化活性(TOF值分别为75和92 h^-1). 作为对比, 本文还合成了采用烷基链为连接基团的SBA-TsDPEN₂₅-Rh, 并以其为基础进一步嫁接了ILs基团, 得到SBA-TsDPEN₂₀-ILBF₄-Rh. 在相同的反应条件下, SBA-ILBF₄-TsDPEN₅₀-Rh表现出更高的催化活性. 上述结果证实了ILs基团在反应过程中起到相转移以及富集氢源甲酸盐的作用, 极大促进了喹哪啶不对称氢转移多相催化体系的活性, 并且ILs基团和手性活性中心在空间距离上的接近更有利于催化活性的提高.
此外, 本文还研究了反应体系pH值对固体催化剂上反应速率的影响, 随着反应的进行, 反应溶液的pH会呈现明显上升的趋势, 导致反应速率减缓以及底物转化受限. 通过在反应过程中加入适量甲酸或者选用浓度更高的缓冲溶液可以有效防止催化过程中反应速率的减慢.
综上可见, 负载手性催化剂中的连接基团对多相手性催化剂的催化性能有重要影响. 通过改变手性配体的连接基团提高手性固体催化剂的催化活性和手性选择性的策略可以拓展到其他多相手性催化体系.

关键词: 多相手性催化, 不对称氢转移, 喹啉衍生物, 咪唑盐, 离子液体, N-(对甲苯磺酰基)-1, 2-二苯基乙二胺

Abstract:

Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge. Herein, we report the immobilization of TsDPEN on SBA-15 with an ionic liquid (IL) linkage via the one-pot reaction of imidazole-TsDPEN-N-Boc with 3-(trimethoxysilyl)propyl bromide in the SBA-15 mesopores. After coordination to Rh, the chiral solid catalysts could efficiently catalyze quinoline transfer hydrogenation, achieving 97% conversion with 93% ee, which was comparable to their homogeneous counterparts. The chiral solid catalyst with the IL linkage afforded much higher turnover frequency than that without the IL linkage (93 h^-1 vs. 33 h^-1), attributed to the phase transfer and formate-enriching ability of the IL linkage. Furthermore, the effect of the pH on the reaction rate of the solid catalyst was investigated, preventing reaction rate retardation during the catalytic process. The tuning of the linkage group is an efficient approach for catalytic activity improvement of immobilized chiral catalysts.

Key words: Heterogeneous asymmetric catalysis, Asymmetric transfer hydrogenation, Quinolines, Imidazolate, Ionic liquid, N-(p-toluenesulfonyl)-1, 2-diphenylethylenediamine

任亦起, 陶琳, 李纯志, Sanjeevi Jayakumar, 李贺, 杨启华. 喹啉及其衍生物的多相不对称氢转移反应[J]. 催化学报, 2021, 42(9): 1576-1585.

Yiqi Ren, Lin Tao, Chunzhi Li, Sanjeevi Jayakumar, He Li, Qihua Yang. Development of efficient solid chiral catalysts with designable linkage for asymmetric transfer hydrogenation of quinoline derivatives[J]. Chinese Journal of Catalysis, 2021, 42(9): 1576-1585.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63764-0

https://www.cjcatal.com/CN/Y2021/V42/I9/1576

图/表 9

Fig. 1. FT-IR spectra of imidazole-TsDPEN-N-Boc (a) and SBA-ILBF4-TsDPEN50 (b); (c) 13C NMR spectrum of imidazole-TsDPEN-N-Boc in CDCl3; (d) 13C CP/TOSS NMR spectrum of SBA-ILBF4-TsDPEN50.

Table 1 Physicochemical parameters of SBA-15, SBA-ILBF4-TsDPENx and SBA-TsDPEN25 before and after coordination with the Rh complex a.

Sample	S_BET (m²/g)	D_p (nm)	V_p (cm³/g)	S content^b (mmol/g)	C content ^b (mmol/g)	Rh content^c (mmol/g)	Weight loss ^d (wt%)	(CH₂)₃Br ^e (wt%)
SBA-15	713	7.5	0.82	—	—	—	—	—
SBA-ILBF₄-TsDPEN₂₀	407 (372)	6.4 (6.4)	0.64 (0.54)	0.16	6.9	(0.09)	17.4	8.4
SBA-ILBF₄-TsDPEN₃₅	315 (250)	6.3 (5.4)	0.46 (0.37)	0.35	12.2	(0.21)	24.7	5.7
SBA-ILBF₄-TsDPEN₅₀	311 (252)	5.4 (5.4)	0.46 (0.38)	0.39	12.7	(0.23)	27.3	5.9
SBA-TsDPEN₂₅	341 (256)	5.4 (5.5)	0.47 (0.36)	0.65	14.4	(0.20)	25.1	—

Fig. 2. (a) TGA curves; (b) N2 sorption isotherms (inset is the pore size distribution curves); (c) XRD patterns; (d) TEM image of SBA-ILBF4-TsDPEN50.

Table 2 Quinaldine asymmetric transfer hydrogenation over homogeneous or heterogeneous catalysts a.

Entry	Catalyst	T (h)	Conv. (%)	ee (%)	TOF (h^-1) ^b
1	Cp^*Rh-TsDPEN	12	95	95	75
2	SBA-ILBF₄-TsDPEN₂₀-Rh	12	86	91	92
3	SBA-ILBF₄-TsDPEN₃₅-Rh	12	86	91	63
4	SBA-ILBF₄-TsDPEN₅₀-Rh	12	84	91	63
5	SBA-ILBF₄-TsDPEN₅₀-Rh	2	62	93	—
6	SBA-ILBF₄-TsDPEN₅₀-Rh ^c	2	62	93	—
7	SBA-ILBF₄-TsDPEN₅₀-Rh ^d	1	38	—	—
8	SBA-ILBF₄-TsDPEN₅₀-Rh ^e	12	93	92	—
9	SBA-ILBF₄-TsDPEN₅₀-Rh ^f	12	96	93	93
10	SBA-TsDPEN₂₅-Rh ^f	12	90	92	33
11	SBA-TsDPEN₂₀-ILBF₄-Rh ^f	12	90	93	60

Fig. 3. (a) Reaction profiles as a function of reaction time of SBA-ILBF4-TsDPENx-Rh and TsDPEN-Rh in quinaldine ATH (5 μmol Rh, 0.5 mmol quinaldine, 5 mmol HCOONa·2H2O and 5.0 mL of 2 M HOAc-NaOAc buffer with an initial pH of 5, 40 °C). (b) Reaction rate and enantioselectivity of quinaldine ATH with different S/C ratios over SBA-ILBF4-TsDPEN50-Rh (5 mmol HCOONa·2H2O, 5.0 mL of 2 M HOAc-NaOAc buffer with an initial pH of 5, 40 °C, 20 min).

Fig. 4. (a) Reaction solution pH with respect to time during quinaldine ATH catalyzed by SBA-ILBF4-TsDPEN50-Rh or SBA-TsDPEN25-Rh (5 μmol Rh, 0.5 mmol quinaldine, 5 mmol HCOONa·2H2O, and 5.0 mL of 2 M/4 M buffer with pH = 5, 40 °C). (b) Reaction profiles as a function of time for SBA-ILBF4-TsDPEN50-Rh and SBA-TsDPEN25-Rh in quinaldine ATH (5 μmol Rh, 0.5 mmol quinaldine, 5 mmol HCOONa·2H2O, and 5.0 mL of 4 M HOAc-NaOAc buffer with an initial pH of 5, 40 °C) and hot filtration test for the ATH reaction with SBA-ILBF4-TsDPEN50-Rh (red dot = after filtering SBA-ILBF4-TsDPEN50-Rh).

Table 3 Asymmetric transfer hydrogenation of substituted quinoline derivatives with SBA-ILBF4-TsDPEN50-Rh a.


Entry	R¹	R²	Conversion ^b (%)	ee ^c (%)
1	Me	Me	87	94
2 ^d	H	Et	89	90
3 ^d	H	n-Pr	87	90
4 ^d	H	n-Bu	88	90
5 ^d	H	n-Pentyl	79	89
6	F	Me	80	90
7 ^e	Br	Me	83	90

Fig. 5. Recyclability of SBA-ILBF4-TsDPEN50-Rh in the asymmetric transfer hydrogenation of quinaldine (the reaction times for cycles 1, 2, 3, 4, and 5 are 2, 2, 3, 6, and 12 h, respectively).

Fig. 6. Scheme 1. SBA-ILBF4-TsDPENx-Rh synthesis and chiral ligand immobilization on SBA-15 via alkane linkage (SBA-TsDPEN25-Rh).

参考文献

[1]	I. Muthukrishnan, V. Sridharan, J. C. Menendez, Chem. Rev., 2019,119, 5057-5191.
[2]	V. Sridharan, P. A. Suryavanshi, J. C. Menendez, Chem. Rev., 2011,111, 7157-7259.
[3]	D.-S. Wang, Q.-A. Chen, S.-M. Lu, Y.-G. Zhou, Chem. Rev., 2012,112, 2557-2590.
[4]	Y.-E. Luo, Y.-M. He, Q.-H. Fan, Chem. Rec., 2016,16, 2693-2707.
[5]	W.-B. Wang, S.-M. Lu, P.-Y. Yang, X.-W. Han, Y.-G. Zhou, J. Am. Chem. Soc., 2003,125, 10536-10537.
[6]	T. Wang, L.-G. Zhuo, Z. Li, F. Chen, Z. Ding, Y. He, Q.-H. Fan, J. Xiang, Z.-X. Yu, A. S. C. Chan, J. Am. Chem. Soc., 2011,133, 9878-9891.
[7]	H. Zhou, Z. Li, Z. Wang, T. Wang, L. Xu, Y. He, Q.-H. Fan, J. Pan, L. Gu, A. S. C. Chan, Angew. Chem. Int. Ed., 2008,47, 8464-8467.
[8]	M. Rueping, A. P. Antonchick, T. Theissmann, Angew. Chem. Int. Ed., 2006,45, 3683-3686.
[9]	D.-W. Wang, W. Zeng, Y.-G. Zhou, Tetrahedron: Asymmetry, 2007,18, 1103-1107.
[10]	C. Wang, C. Li, X. Wu, A. Pettman, J. Xiao, Angew. Chem. Int. Ed., 2009,48, 6524-6528.
[11]	V. Parekh, J. A. Ramsden, M. Wills, Tetrahedron: Asymmetry, 2010,21, 1549-1556.
[12]	Q.-S. Guo, D.-M. Du, J. Xu, Angew. Chem. Int. Ed., 2008,47, 759-762.
[13]	R. Noyori, S. Hashiguchi, Acc. Chem. Res., 1997,30, 97-102.
[14]	Q.-H. Fan, Y.-M. Li, A. S. C. Chan, Chem. Rev., 2002,102, 3385-3466.
[15]	M. Heitbaum, F. Glorius, I. Escher, Angew. Chem. Int. Ed., 2006,45, 4732-4762.
[16]	D. Zhao, K. Ding, ACS Catal., 2013,3, 928-944.
[17]	R. Liu, T. Cheng, L. Kong, C. Chen, G. Liu, H. Li, J. Catal., 2013,307, 55-61.
[18]	X. Zhang, Y. Zhao, J. Peng, Q. Yang, Green Chem., 2015,17, 1899-1906.
[19]	X. Shu, R. Jin, Z. Zhao, T. Cheng, G. Liu, Chem. Commun., 2018,54, 13244-13247.
[20]	F. Zhou, X. Hu, M. Gao, T. Cheng, G. Liu, Green Chem., 2016,18, 5651-5657.
[21]	S. Bai, H. Yang, P. Wang, J. Gao, B. Li, Q. Yang, C. Li, Chem. Commun., 2010,46, 8145-8147.
[22]	T. Takeda, M. Terada, J. Am. Chem. Soc., 2013,135, 15306-15309.
[23]	G. Kang, S. Lin, A. Shiwakoti, B. Ni, Catal. Commun., 2014,57, 111-114.
[24]	P. N. Liu, P. M. Gu, F. Wang, Y. Q. Tu, Org. Lett., 2004,6, 169-172.
[25]	S. Jayakumar, H. Li, L. Tao, C. Li, L. Liu, J. Chen, Q. Yang, ACS Sustain. Chem. Eng., 2018,6, 9237-9245.
[26]	J. C. Lassegues, J. Grondin, D. Cavagnat, P. Johansson, J. Phys. Chem. A, 2009,113, 6419-6421.
[27]	L. Tao, C. Li, Y. Ren, H. Li, J. Chen, Q. Yang, Chin. J. Catal., 2019,40, 1548-1556.
[28]	L. Tao, Y. Ren, C. Li, H. Li, J. Liu, Q. Yang, Asian J. Org. Chem., 2020,9, 1623-1630.
[29]	L. Tao, Y. Ren, C. Li, H. Li, X. Chen, L. Liu, Q. Yang, ACS Catal., 2020,10, 1783-1791.
[30]	D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science, 1998,279, 548-552.

喹啉及其衍生物的多相不对称氢转移反应

Development of efficient solid chiral catalysts with designable linkage for asymmetric transfer hydrogenation of quinoline derivatives

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 9

参考文献

相关文章 15

编辑推荐

Metrics

[1]	Ernest Pahuyo Delmo, 王忆安, 王菁, 朱尚乾, 李铁怀, 秦雪苹, 田一博, 赵青蓝, Juhee Jang, 王一诺, 谷猛, 张莉莉, 邵敏华. 金属有机框架-离子液体混合催化剂用于电化学还原二氧化碳生成甲烷[J]. 催化学报, 2022, 43(7): 1687-1696.
[2]	茆卉, 杨浩然, 柳金池, 张帅, 刘大亮, 吴琼, 孙文平, 宋溪明, 马天翼. 基于聚(两性离子液体)功能化聚吡咯/氧化石墨烯的独特MoS₂-SnS₂异质纳米片及其改善的氮还原电活性[J]. 催化学报, 2022, 43(5): 1341-1350.
[3]	于子勋, 刘畅, 邓业煜, 李默涵, 厍芳馨, Leo Lai, 陈元, 魏力. 利用离子液体界面工程实现非均相分子催化剂高效生产双氧水[J]. 催化学报, 2022, 43(5): 1238-1246.
[4]	陈必华, 丁桐, 邓熹, 王鑫, 张大卫, 马三罐, 张永亚, 倪兵, 高国华. 酸性聚离子液体溶胀诱导自组装形成类蜂窝状固体酸催化剂及其高效催化水解反应[J]. 催化学报, 2021, 42(2): 297-309.
[5]	赵佳, 王赛赛, 王柏林, 岳玉学, 金春晓, 陆金跃, 方正, 庞祥雪, 丰枫, 郭伶伶, 潘志彦, 李小年. 乙炔氢氯化反应中的负载金-离子液体催化剂: 离子态金物种的稳定机制[J]. 催化学报, 2021, 42(2): 334-346.
[6]	李凯, 季梦夏, 陈蓉, 姜琪, 夏杰祥, 李华明. 氮磷共掺杂石墨烯量子点/Bi₅O₇I复合材料的构筑及增强的光催化降解性能[J]. 催化学报, 2020, 41(8): 1230-1239.
[7]	李明浩, 吴丰田, 顾彦龙. Brönsted酸性离子液体催化α-羟基丙酮和2-苯基吲哚反应合成苯并[a]咔唑[J]. 催化学报, 2019, 40(8): 1135-1140.
[8]	陈翰祥, 曾洁, 陈敏东, 陈志刚, 季梦夏, 赵君泽, 夏杰祥, 李华明. 反应型离子液体辅助合成钒酸铁介孔纳米棒及其增强可见光光催化活性[J]. 催化学报, 2019, 40(5): 744-754.
[9]	王国芹, 宋河远, 李瑞云, 李臻, 陈静. 新型高效Brönsted酸性离子液体催化剂体系催化烯烃齐聚反应[J]. 催化学报, 2018, 39(6): 1110-1120.
[10]	李赫楠, 徐雅楠, Hansinee Sitinamaluwa, Kimal Wasalathilake, Dilini Galpaya, 闫澄. 石墨化氮化碳负载Cu纳米颗粒用作高效氧还原电催化剂[J]. 催化学报, 2017, 38(6): 1006-1010.
[11]	张伟, 韩峰, 童进, 夏春谷, 刘建华. 1,1,3,3-四烷基胍羰基钴离子液体:高效可循环利用的环氧化合物羰基化反应催化新材料[J]. 催化学报, 2017, 38(5): 805-812.
[12]	宋河远, 康美荣, 金福祥, 王国芹, 李臻, 陈静. Brønsted酸性离子液体催化缩醛化反应合成聚甲氧基二烷基醚[J]. 催化学报, 2017, 38(5): 853-861.
[13]	赵聪, 陈圣新, 张瑞锐, 李自航, 刘瑞霞, 任保增, 张锁江. 环境友好型离子液体催化环氧丙烷反应合成丙二醇醚[J]. 催化学报, 2017, 38(5): 879-889.
[14]	孙玮, 徐菲, 成卫国, 孙剑, 宁国庆, 张锁江. 季铵类离子液体催化熔融缩聚反应合成异山梨醇基聚碳酸酯[J]. 催化学报, 2017, 38(5): 908-917.
[15]	王荷芳, 贾丽媛, 胡荣斌, 高美丹, 王延吉. 多功能Na₂WO₄-离子液体催化体系催化环己醇一锅合成己内酰胺[J]. 催化学报, 2017, 38(1): 58-64.