CuFe2O4纳米粒子催化芳香酮的不对称硅氢化反应

doi:10.7503/cjcu20150650

摘要/Abstract

摘要：

分别采用共沉淀法、溶胶-凝胶法和溶剂热法制备得到CuFe₂O₄纳米粒子, 以(R)-联萘二苯基膦[(R)-BINAP]为手性配体、聚甲基氢硅氧烷(PMHS)为硅氢化试剂, 将制得的CuFe₂O₄纳米粒子用于催化芳香酮的不对称硅氢化反应. 结果表明, 溶剂热法能制得分散性好、粒径小且分布均匀的CuFe₂O₄纳米球, 其催化活性明显优于其它2种方法. 在添加剂t-BuOK和t-BuOH的共同作用下, CuFe₂O₄纳米粒子的催化活性得以明显改善, 最终得到一种高效的非均相催化体系CuFe₂O₄/t-BuOK/t-BuOH. 在室温和空气氛围下, 用于催化芳香酮的不对称硅氢化反应, 底物转化率和产物对映体过量值分别高达99%和92%. 研究证实底物芳环上取代基的电子效应和空间位阻明显影响不对称硅氢化反应的结果. CuFe₂O₄纳米催化剂在外加磁场的作用下能较易从反应体系中分离回收, 且催化剂经4次循环利用后仍具有较高的催化活性.

关键词: 不对称硅氢化反应, 芳香酮, CuFe2O4纳米粒子, 聚甲基氢硅氧烷

Abstract:

CuFe₂O₄ nanoparticles were synthesized by coprecipitation, sol-gel and solvothermal methods, respectively. The asymmetric hydrosilation of aromatic ketones was catalyzed by CuFe₂O₄ nanoparticles, employing (R)-BINAP[2,2'-bis(diphenylphosphino)-1,1'-binaphthalene] as chiral ligand and polymethylhydrosiloxane as hydrosilating reagent. The results showed that compared to the others, the CuFe₂O₄ nanoparticles prepared by solvothermal method had spherical shape, small size, better dispersion, uniform distribution and excellent catalytic activities. Meanwhile, it was found that the catalytic activity of the CuFe₂O₄ nanoparticles was significantly improved with the addition of t-BuOK and t-BuOH. An efficient heterogeneous catalytic system CuFe₂O₄/t-BuOK/t-BuOH was finally obtained. Under room temperature and air atmosphere, the conversion of the aromatic ketones and the enantiomeric excesses of the (R)-1-arylethanols were up to 99% and 92%, respectively, with the heterogeneous catalytic system. It was also confirmed that the electronic effect and steric hindrance of the groups on the aromatic ring distinctly affected the results of hydrosilation. And a possible mechanism was presented to explain the influence of some key factors on the reaction. Furthermore, it was demonstrated that the CuFe₂O₄ nanocatalyst could be easily separated from reaction system under an external magnetic field. And after recycling for four times, the catalyst could also have a high catalytic activity for the asymmetric hydrosilation.

Key words: Asymmetric hydrosilation, Aromatic ketone, CeFe2O4 nanoparticles, Polymethylhydrosiloxane

中图分类号:

TrendMD:

朱洁莲, 夏晓峰, 梁敏婷, 刘湘, 李和兴. CuFe₂O₄纳米粒子催化芳香酮的不对称硅氢化反应. 高等学校化学学报, 2016, 37(3): 539.

ZHU Jielian, XIA Xiaofeng, LIANG Minting, LIU Xiang, LI Hexing. Asymmetric Hydrosilation of Aromatic Ketones Catalyzed by CuFe₂O₄ Nanoparticles^†. Chem. J. Chinese Universities, 2016, 37(3): 539.

图/表 9

Fig.1 SEM images of CuFe2O4 prepared by different methods(A) Coprecipitation method; (B) sol-gel method; (C) solvothermal method.

Fig.2 XRD patterns of CuFe2O4 prepared by sol-gel(a), coprecipitation(b) and solvothermal(c) methods

Table 1 Asymmetric hydrosilation of acetophenone catalyzed by CuFe2O4 nanoparticles via different methodsa

Entry	Synthetic method of CuFe₂O₄	Temperature/℃	Time/h	Conversion(%)	e.e.(%)^b
1	Coprecipitation	25	14	71	77
2	Coprecipitation	55	14	99	72
3	Sol-gel	25	14	37	75
4	Sol-gel	55	14	70	72
5	Solvothermal	25	2	99	77

Table 2 Effects of additives on the asymmetric hydrosilation of acetophenonea

Entry	n(t-BuOK)/mmol	n(t-BuOH)/mmol	Conversion(%)	e.e.^b (%)
1			66	76
2	0.03		89	77
3	0.03	3	99	77
4		3	24	75
5^c	0.03	3	<5

Table 3 Effects of substrates on the asymmetric hydrosilationa

Entry	R	Time/h	Conversion(%)	e.e.^b(%)	Entry	R	Time/h	Conversion(%)	e.e.^b(%)
1	H	2	99	77	6	4'-CH₃	2	56	77
2	2'-Cl	2	99	62	7	4'-CH₃	10	85	78
3	3'-Cl	2	99	81	8	4'-OCH₃	2	35	80
4	4'-Cl	2	99	87	9	4'-OCH₃	20	81	79
5	4'-NO₂	2	99	92

Fig.3 Magnetic separation of CuFe2O4 nanoparticles

Table 4 Recycling of CuFe2O4 nanoparticles catalyst for the asymmetric hydrosilation of acetophenonea

Entry	Times of recycling	Catalyst recovery(%)	Conversion(%)	e.e.^b(%)
1	0		99	77
2	1	89	99	77
3	2	90	94	77
4	3	89	88	76
5	4	91	80	77

Fig.4 SEM images of the original(A) and reclaimed(B) CuFe2O4 nanoparticles

Fig.5 Plausible mechanism of the asymmetric hydrosilation of aromatic ketones catalyzed by CuFe2O4 nanoparticles

参考文献 33

[1]	Denard C. A., Hartwig J. F., Zhao H., ACS Catalysis, 2013, 3(12), 2856—2864
[2]	Liu X., Pan Z. G., Xu J. H., Prog. Chem., 2011, 23(5), 87—96
	(刘湘, 潘争光, 许建和. 化学进展, 2011, 23(5), 87—96)
[3]	Zhang X. C., Wu Y., Yu F., Wu F. F., Wu J., Chan A. S., Chemistry,2009, 15(24), 5888—5891
[4]	Riant O., Mostefai N., Courmarcel J., Synthesis-Stuttgart,2004, 18(12), 2943—2958
[5]	Perez M., Qu Z. W., Caputo C. B., Podgorny V., Hounjet L. J., Hansen A., Dobrovetsky R., Grimme S., Stephan D. W., Chem. Eur. J., 2015, 21(17), 6491—6500
[6]	Kawabata S., Tokura H., Chiyojima H., Okamoto M., Sakaguchi S., Adv. Synth. Catal., 2012, 354(5), 807—812
[7]	Moser R., Boskovic Z. V., Crowe C. S., Lipshutz B. H., J. Am. Chem. Soc., 2010, 132(23), 7852—7853
[8]	Yao J. S. Wu Y. S., Chem. J. Chinese Universities, 2002, 23(1), 68—70
	(姚金水, 吴佑实. 高等学校化学学报, 2002, 23(1), 68—70)
[9]	Wu F. F., Zhou J. N., Fang Q., Hu Y. H., Li S., Zhang X. C., Chan A. S., Wu J., Chem. Asian J., 2012, 7(11), 2527—2530
[10]	Liu L. J., Wang F. J., Shi M., Organometallics,2009, 28(15), 4416—4420
[11]	Issenhuth J. T., Dagorne S., Bellemin-Laponnaz S., Adv. Synth. Catal., 2006, 348(14), 1991—1994
[12]	Sirol S., Courmarcel J., Mostefai N., Riant O., Org. Lett., 2001, 3(5), 4111—4113
[13]	Ji Y. G., Wu L., Fan Q. H., Acta Chim. Sinica, 2014, 72(7), 798—808
	(季益刚, 吴磊, 范青华. 化学学报, 2014, 72(7), 798—808)
[14]	Ranganath K. V. S., Glorius F., Catal. Sci. Technol., 2011, 1(1), 13—22
[15]	Lee C. T., Lipshutz B. H., Org. Lett., 2008, 10(19), 4187—4190
[16]	Lipshutz B. H., Frieman B. A., Tomaso A. E. Jr., Angew. Chem. Int. Ed., 2006, 45(8), 1259—1264
[17]	Kantam M. L., Yadav J., Laha S., Srinivas P., Sreedhar B., Figueras F., J. Org. Chem., 2009, 74(12), 4608—4611
[18]	Kantam M. L., Laha S., Yadav J., Likhar P. R., Sreedhar B., Jha S., Bhargava S., Udayakiran M., Jagadeesh B., Org. Lett., 2008, 10(19), 4391—4391
[19]	Kantam M. L., Laha S., Yadav J., Likhar P. R., Sreedhar B., Choudary B. M., Adv. Synth. Catal., 2007, 349(10), 1797—1802
[20]	Issenhuth J. T., Dagorne S., Bellemin-Laponnaz S., C. R. Chim., 2010, 13(3), 353—357
[21]	Lee D. W., Yun J., Tetrahedron Lett., 2004, 45(28), 5415—5417
[22]	Pandya P. B., Joshi H. H., kulkarni R. G., J. Mater. Sci. Lett., 1991, 10(8), 474—476
[23]	Li M., Li B., Xia H. F., Ye D., Wu J., Shi Y., Green Chemistry, 2014, 16(5), 2680—2688
[24]	Li B., Li M., Yao C., Shi Y., Ye D., Wu J., Zhao D., J. Mater. Chem. A, 2013, 1(23), 6742—6749
[25]	Yang H., Yan J., Lu Z., Cheng X., Tang Y., J. Alloys Compd., 2009, 476(1/2), 715—719
[26]	Tao S. W., Gao F., Liu X. Q., Sϕrensen O. T., Mater. Sci. Eng. B, 2000, 77(2), 172—176
[27]	Zhang W., Quan B., Lee C., Park S. K., Li X., Choi E., Diao G., Piao Y., ACS Appl. Mater. Interfaces, 2015, 7(4), 2404—2414
[28]	Yang L. X., Xu Y. B., Jin R. C., Wang F., Yin P., Li G. H., Xu C. P., Pan L. B., Ceram. Int., 2015, 41(2, Part A), 2309—2317
[29]	Qi S. B., Li M., Li S., Zhou J. N., Wu J. W., Yu F., Zhang X. C., Chan A. S., Wu J., Org. Biomol. Chem., 2013, 11(6), 929—937
[30]	Liu X., Zhang B. L., Xia Y. M., Xu J. H., Acta Chim. Sinica, 2009, 67(13), 1492—1496
	(刘湘, 张宝立, 夏咏梅, 许建和. 化学学报, 2009, 67(13), 1492—1496)
[31]	Kantam M. L., Laha S., Yadav J., Likhar P. R., Sreedhar B., Jha S., Bhargava S., Udayakiran M., Jagadeesh B., Org. Lett., 2008, 10(14), 2979—2982
[32]	Shimizu H., Igarashi D., Kuriyama W., Yusa Y., Sayo N., Saito T., Org. Lett., 2007, 9(9), 1655—1657
[33]	Zhang X. C., Wu F. F., Li S., Zhou J. N., Wu J., Li N., Fang W., Lam K. H., Chan A. S. C., Adv. Synth. Catal., 2011, 353(9), 1457—1462

CuFe₂O₄纳米粒子催化芳香酮的不对称硅氢化反应

Asymmetric Hydrosilation of Aromatic Ketones Catalyzed by CuFe₂O₄ Nanoparticles^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 33

相关文章 4

编辑推荐

Metrics

本文评价

[1]	赵齐齐, 梁苗苗, 马洋洋, 李晓凯, 朱华结, 李婉. 新轴手性N,N-Dioxide Biscarbolin衍生物催化酮亚胺的不对称硅氢化反应[J]. 高等学校化学学报, 2017, 38(7): 1192.
[2]	李霄, 高立国, 弓莹, 马亚军, 马向荣. 杂双金属复合物ZABDP催化芳香酮与芳香醛的直接不对称Aldol反应[J]. 高等学校化学学报, 2017, 38(5): 778.
[3]	潘恩德, 李岩云, 董振荣, 陈建珊, 李宝珠, 章慧, 高景星. 芳香酮的高效对映选择性转移氢化[J]. 高等学校化学学报, 2003, 24(9): 1615.
[4]	姚金水, 吴佑实. 铑(I)催化的不对称硅氢化反应合成手性2-氨基-1-芳基乙醇研究[J]. 高等学校化学学报, 2002, 23(1): 68.