通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物

引用本文: 李猛, 胡晨晖, 江春涛, 杨惠, 陈才, 侯文华, 陈静. 通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物[J]. 无机化学学报, 2013, 29(11): 2339-2346. doi: 10.3969/j.issn.1001-4861.2013.00.385 shu

Citation: LI Meng, HU Chen-Hui, JIANG Chun-Tao, YANG Hui, CHEN Cai, HOU Wen-Hua, CHEN Jing. Immobilization of Chiral Mn(salen) Complex on MCM-41 via Functionalizing with Benzyl Sulphonic Acid[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(11): 2339-2346. doi: 10.3969/j.issn.1001-4861.2013.00.385 shu

通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物

李猛 ^1, ,
胡晨晖 ^2, ,
江春涛 ^1, ,
杨惠 ^1, ,
陈才 ^1, ,
侯文华 ^2, ,
陈静 ^1,

基金项目:
国家自然科学基金(No.21073084) (No.21073084)

江苏省自然科学基金(BK2011438) (BK2011438)

国家基础研究973项目(2009CB623504) (2009CB623504)

南京工业大学青年教师学术基金(No.39704013)资助项目。 (No.39704013)

摘要: 首先通过两步后合成处理,在MCM-41上接枝苄基磺酸;然后,以苄基磺酸为过渡产物,用手性Mn(salen)配合物修饰处理,得到了苄基磺酸轴向负载手性Mn(salen)配合物的MCM-41;实现了在廉价且温和条件下均相手性Mn(salen)催化剂的非均相化。采用X射线衍射(XRD)、低温N₂吸附-脱附、红外光谱、热重-差示扫描量热(TG-DSC)分析、电感耦合等离子体发射光谱(ICP)和酸度滴定等对样品进行了表征。结果表明,手性Mn(salen)配合物成功固载在MCM-41上,且MCM-41的介孔结构和Mn(salen)配合物的手性特征仍然保留。以间氯过氧苯甲酸为氧化剂,考察了所得固载型催化剂对α-甲基苯乙烯的不对称环氧化催化性能,结果表明在0℃反应2h,催化剂用量为0.02mmol,无需加入轴向配体N-甲基吗啉氮氧化物(NMO)的条件下对映体过量(enantiomericexcess,e.e.)值可达99%以上,转化率为77%。归因于苄基磺酸基起到了很好的轴向配体作用。经适当处理,固载型催化剂在循环使用5次后e.e.值依然有71%,表现出较好的活性和重复使用性能。

关键词:

MCM-41;手性Mn(salen)配合物;固载型催化剂;不对称环氧化

English

Immobilization of Chiral Mn(salen) Complex on MCM-41 via Functionalizing with Benzyl Sulphonic Acid

1.
1 School of Science, Nanjing University of Technology, Nanjing 210009, China;
Received Date: 31 March 2013
Fund Project:
国家自然科学基金(No.21073084)

江苏省自然科学基金(BK2011438)

国家基础研究973项目(2009CB623504)

南京工业大学青年教师学术基金(No.39704013)资助项目。

Abstract: MCM-41 was first functionalized with benzyl sulphonic acid using a post-synthetic procedure and then modified with chiral Mn(salen) complex to prepare a heterogeneous chiral Mn(salen) catalyst under cheap and mild conditions. The chiral Mn(salen) complex was axially immobilized into MCM-41 via the organic benzyl sulfonic groups. The catalyst was characterized by XRD, N₂ adsorption-desorption, FTIR, TG-DSC, ICP and acid capacity titration. The results show that the chiral Mn(salen) complex has been supported on MCM-41, and the mesoporous structure of MCM-41 and the chiral structure of Mn(salen) are still remained. The supported catalyst was applied to the asymmetric epoxidation of α-methylstyrene using m-chloroperbenzoic acid as an oxidant at 0 ℃, and showed excellent performance with a conversion of 77% and e.e. (enantiomeric excess) value above 99% after a rather short reaction time of 2 h in the absence of NMO (N-Methylmorpholine-N-Oxide). The benzyl sulphonic acid groups play a very good axial ligand function. By treating properly, the e.e. value was still 71% after the supported catalyst was reused 5 times.

Key words:

MCM-41;chiral Mn(salen) complex;supported catalyst;asymmetric epoxidation

1. [1] Cavallo L, Jacobsen H. Angew. Chem. Int. Ed., 2000,39(3): 589-592[1] Cavallo L, Jacobsen H. Angew. Chem. Int. Ed., 2000,39(3): 589-592
2. [2] McGarrigle E M, Gilheany D G. Chem. Rev., 2005,105(5): 1563-1602[2] McGarrigle E M, Gilheany D G. Chem. Rev., 2005,105(5): 1563-1602
3. [3] LUO Yun-Fei (罗云飞), ZOU Xiao-Chuan(邹晓川), FU Xiang-Kai(傅相锴). Scientia Sinica Chimica (Zhongguo Kexue: Huaxue), 2011,41(3):433-450[3] LUO Yun-Fei (罗云飞), ZOU Xiao-Chuan(邹晓川), FU Xiang-Kai(傅相锴). Scientia Sinica Chimica (Zhongguo Kexue: Huaxue), 2011,41(3):433-450
4. [4] Krege C T, Lenonowicz M E, Beck J S, et al. Nature, 1992, 359(6397):710-712[4] Krege C T, Lenonowicz M E, Beck J S, et al. Nature, 1992, 359(6397):710-712
5. [5] Hoffmann F, Cornelius M, Morell J, et al. Angew. Chem. Int. Ed., 2006,45:3216-3251[5] Hoffmann F, Cornelius M, Morell J, et al. Angew. Chem. Int. Ed., 2006,45:3216-3251
6. [6] Li C. Catal. Rev.: Sci. & Eng., 2004,46(3/4):419-492[6] Li C. Catal. Rev.: Sci. & Eng., 2004,46(3/4):419-492
7. [7] Li C, Zhang H D, Jiang D M, et al. Chem. Commun., 2007: 547-558[7] Li C, Zhang H D, Jiang D M, et al. Chem. Commun., 2007: 547-558
8. [8] Zhang H D, Zhang Y M, Li C. J. Catal., 2006,238(2):369-381[8] Zhang H D, Zhang Y M, Li C. J. Catal., 2006,238(2):369-381
9. [9] Zhao Ji-Quan(赵继全), Zhang Ya-Ran(张雅然), Zhang Yue-Cheng(张月成). Chinese J. Catal. (Cuihua Xuebao), 2007,28 (1):85-90[9] Zhao Ji-Quan(赵继全), Zhang Ya-Ran(张雅然), Zhang Yue-Cheng(张月成). Chinese J. Catal. (Cuihua Xuebao), 2007,28 (1):85-90
10. [10]CHEN Jing(陈静), HAN Mei(韩梅), SUN Rui(孙蕊), WANG Jin-Tang(王锦堂). Chinese J. Inorg. Chem.(Wuji Huaxue Xuebao), 2006,22(9):1568-1572[10]CHEN Jing(陈静), HAN Mei(韩梅), SUN Rui(孙蕊), WANG Jin-Tang(王锦堂). Chinese J. Inorg. Chem.(Wuji Huaxue Xuebao), 2006,22(9):1568-1572
11. [11]Larrow J F, Jacobsen E N, Gao Y, et al. J. Org. Chem., 1994,59(7):1939-1942[11]Larrow J F, Jacobsen E N, Gao Y, et al. J. Org. Chem., 1994,59(7):1939-1942
12. [12]Zhang H D, Li C. Tetrahedron., 2006,62(28):6640-6649[12]Zhang H D, Li C. Tetrahedron., 2006,62(28):6640-6649
13. [13]Dufaud V, Davis M E. J. Am. Chem. Soc., 2003,125(31): 9403-9413[13]Dufaud V, Davis M E. J. Am. Chem. Soc., 2003,125(31): 9403-9413
14. [14]RUN Ming-Tao(闰明涛), ZHANG Da-Yu(张大余), WU Gang (吴刚). Chinese J. Inorg. Chem.(Wuji Huaxue Xuebao), 2005,21(8):1165-1169[14]RUN Ming-Tao(闰明涛), ZHANG Da-Yu(张大余), WU Gang (吴刚). Chinese J. Inorg. Chem.(Wuji Huaxue Xuebao), 2005,21(8):1165-1169
15. [15]XU Ru-Ren(徐如人), PANG Wen-Qin(庞文琴). Zeolites and Porous Materials Chemistry (分子筛与多孔材料化学). Beijing: Science Press, 2004:146[15]XU Ru-Ren(徐如人), PANG Wen-Qin(庞文琴). Zeolites and Porous Materials Chemistry (分子筛与多孔材料化学). Beijing: Science Press, 2004:146
16. [16]CHANG Yan(常燕), JIN Sheng-Ming (金胜明), GUAN Hao-Yuan(关豪元). et al. J. Cent. South. Univ.: Science and Technology(Zhongnan Daxue Zirankexue Ban), 2008,39 (2):265-267[16]CHANG Yan(常燕), JIN Sheng-Ming (金胜明), GUAN Hao-Yuan(关豪元). et al. J. Cent. South. Univ.: Science and Technology(Zhongnan Daxue Zirankexue Ban), 2008,39 (2):265-267
17. [17]Luechinger M, Frunz L, Prins R, et al. Micropor. Mesopor. Mater., 2003,64(1/2/3):203-211[17]Luechinger M, Frunz L, Prins R, et al. Micropor. Mesopor. Mater., 2003,64(1/2/3):203-211
18. [18]Ng E P, Subari S N M, Marie O. et al. Appl. Catal. A, 2013,450:34-41[18]Ng E P, Subari S N M, Marie O. et al. Appl. Catal. A, 2013,450:34-41
19. [19]Zhang H D, Xiang S, Li C. Chem. Commun., 2005:1209-1211[19]Zhang H D, Xiang S, Li C. Chem. Commun., 2005:1209-1211
20. [20]Huang J, Fu X K, Wang G. et al. Dalton Trans., 2012,41: 10661-10669[20]Huang J, Fu X K, Wang G. et al. Dalton Trans., 2012,41: 10661-10669
21. [21](a) Liao S H, List B. Angew. Chem. Int. Ed., 2010,49:628-631[21](a) Liao S H, List B. Angew. Chem. Int. Ed., 2010,49:628-631
22. [22]
  (b) Hu C H, Zhang L H, Hou W H. Catal. Commun. 2012. 28:111-115(b) Hu C H, Zhang L H, Hou W H. Catal. Commun. 2012. 28:111-115
23. [23]
  (c) Huang X M, Fu X K, Jia Z Y. et al. Catal. Sci. Technol., 2013,3:415-424(c) Huang X M, Fu X K, Jia Z Y. et al. Catal. Sci. Technol., 2013,3:415-424
24. [22]ZOU Xiao-Chuan(邹晓川), FU Xiang-Kai(傅相锴), LUO Yun-Fei(罗云飞). Acta Chim. Sin.(Huaxue Xuebao), 2011,69 (4):431-437[22]ZOU Xiao-Chuan(邹晓川), FU Xiang-Kai(傅相锴), LUO Yun-Fei(罗云飞). Acta Chim. Sin.(Huaxue Xuebao), 2011,69 (4):431-437
25. [23](a) Hosoya N, Hatayama A, Katusuki T, et al. Synlett., 1993: 641-645[23](a) Hosoya N, Hatayama A, Katusuki T, et al. Synlett., 1993: 641-645
26. [26]
  (b) Hosoya N, Hatayama A, Katusuki T, et al. Tetrahedron, 1994,50:4311-4322(b) Hosoya N, Hatayama A, Katusuki T, et al. Tetrahedron, 1994,50:4311-4322
27. [24]HU Yue-Fei(胡跃飞), LIN Guo-Qiang(林国强). Modern Organic Reaction:Vol.1(现代有机反应:氧化反应). Beijing: Chemical Industry Press, 2008:132[24]HU Yue-Fei(胡跃飞), LIN Guo-Qiang(林国强). Modern Organic Reaction:Vol.1(现代有机反应:氧化反应). Beijing: Chemical Industry Press, 2008:132

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通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物

English

Immobilization of Chiral Mn(salen) Complex on MCM-41 via Functionalizing with Benzyl Sulphonic Acid

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

通过接枝苄基磺酸在MCM-41上固载手性Mn(salen)配合物

English

Immobilization of Chiral Mn(salen) Complex on MCM-41 via Functionalizing with Benzyl Sulphonic Acid

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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