离子液体功能化手性salen Mn(Ⅲ)配合物不对称催化仲醇氧化动力学拆分反应

doi:10.7503/cjcu20130374

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (2): 297.doi: 10.7503/cjcu20130374

离子液体功能化手性salen Mn(Ⅲ)配合物不对称催化仲醇氧化动力学拆分反应

黎成勇¹, 谭蓉¹(), 赵江峰¹, 银董红^1,²

1. 湖南师范大学精细催化合成研究所, 长沙410081
2. 湖南中烟工业有限责任公司技术研发中心, 长沙410014

收稿日期:2013-04-24 出版日期:2014-02-10 发布日期:2013-11-01
作者简介:联系人简介: 谭蓉, 女, 博士, 副教授, 主要从事有机功能材料研究. E-mail:yiyangtanrong@126.com
基金资助:
国家自然科学基金(批准号: 21003044, 20973057)和湖南省自然科学基金(批准号: 10JJ6028)资助

Ionic Liquid-functionalized Chiral salen Mn(Ⅲ) Complex for Asymmetric Oxidative Kinetic Resolution of Racemic Secondary Alcohols^†

LI Chengyong¹, TAN Rong^1,^*(), ZHAO Jiangfeng¹, YIN Donghong^1,²

1. Institute of Fine Catalysis and Synthesis, Hunan Normal University, Changsha 410081, China
2. Research and Development Center, China Tobacco Hunan Industrial Corporation, Changsha 410014, China

Received:2013-04-24 Online:2014-02-10 Published:2013-11-01
Contact: TAN Rong E-mail:yiyangtanrong@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21003044, 20973057) and the Natural Science Foundation of Hunan Province, China(No.10JJ6028)

摘要/Abstract

摘要：

采用共价键联法, 将亲水性咪唑类离子液体结构引入手性salen Mn(Ⅲ)配合物的C5位, 制备了离子液体功能化手性salen Mn(Ⅲ)配合物. 傅里叶变换红外光谱、紫外光谱和旋光分析等结果表明, 咪唑类离子液体结构已嫁接到手性salen Mn(Ⅲ)配合物结构中, 且嫁接过程未破坏催化活性中心. 在以PhI(OAc)₂为氧化剂, H₂O/CH₂Cl₂为溶剂的(+/-)-α-甲基苯甲醇不对称氧化动力学拆分反应中, 该催化剂表现出比传统手性salen Mn(Ⅲ)催化剂更高的催化活性, 仲醇的转化率达到63%以上, 对映选择性为99%, 拆分效率为18.3%. 可通过调变溶剂实现催化剂的分离并重复使用3次以上. 实验结果表明, 亲水性咪唑离子液体可改善水相反应传质问题且有利于稳定催化活性中间体, 从而提高催化活性及稳定性.

关键词: 对映选择性, 离子液体, 手性salen Mn(Ⅲ)配合物, 不对称氧化动力学拆分, 仲醇

Abstract:

Hydrophilic imidazolium-based ionic liquid(IL) was introduced into the framework of the chiral salen Mn(Ⅲ) complex by covalent linkage, which provided a ionic liquid-functionalized chiral salen Mn(Ⅲ) complex. Fourier transform infrared spectrometry, UV-Vis and thermal analysis results showed that the chiral salen Mn(Ⅲ) complex was modified with the IL moiety with the intact active site. The catalytic performance of IL-functionalized chiral salen Mn(Ⅲ) complex in the asymmetric oxidation kinetic resolution(OKR) of secondary alcohols was investigated. It was found that the surfactant-type complex showed higher catalytic activity than neat chiral salen Mn(Ⅲ) complex. Secondary alcohol conversion was more than 63%, enantioselective could reach 99% and separation efficiency was 18.3%. Catalyst could be facilely recovered from the reaction system for reuse 3 times by controlling solvent. The hydrophilic imidazolium-based IL was thought to improve the mass transfer associated with the aqueous reaction and stabilize the transition state, which in turns enhanced the activity and stability of the catalysts.

Key words: Enantioselectivity, Ionic liquid, Chiral salen Mn(Ⅲ) complex, Oxidation kinetic resolution, Secondary alcohol

中图分类号:

O621
O643

TrendMD:

黎成勇, 谭蓉, 赵江峰, 银董红. 离子液体功能化手性salen Mn(Ⅲ)配合物不对称催化仲醇氧化动力学拆分反应. 高等学校化学学报, 2014, 35(2): 297.

LI Chengyong, TAN Rong, ZHAO Jiangfeng, YIN Donghong. Ionic Liquid-functionalized Chiral salen Mn(Ⅲ) Complex for Asymmetric Oxidative Kinetic Resolution of Racemic Secondary Alcohols^†. Chem. J. Chinese Universities, 2014, 35(2): 297.

图/表 7

Fig.1 UV-Vis spectra of complex 1(a) and traditional chiral salen Mn(Ⅲ) complex(b)

Table 1 Oxidation kinetic resolution of α-methyl benzyl alcohol over complex 1a

Entry	Catalyst	Catalyst amount(%)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1			60	0
2	Complex 1	0.25	58	69	5.9
3	Complex 1	0.5	62	90	10.0
4	Complex 1	1	63	>99	18.3
5	Complex 1	1.5	63	>99	18.3
6	Complex 2	1	59	56	3.8
7	Neat complex	1	61	97	16.9

Table 1 Oxidation kinetic resolution of α-methyl benzyl alcohol over complex 1a

Entry	Catalyst	Catalyst amount(%)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1			60	0
2	Complex 1	0.25	58	69	5.9
3	Complex 1	0.5	62	90	10.0
4	Complex 1	1	63	>99	18.3
5	Complex 1	1.5	63	>99	18.3
6	Complex 2	1	59	56	3.8
7	Neat complex	1	61	97	16.9

Table 2 Oxidation kinetic resolution of α-methyl benzyl alcohol over complex 1 with various additivesa

Entry	Additive	Additive amount(%)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1			16	0
2	KBr	4	55	69	7.2
3	KBr	6	63	>99	18.3
4	KBr	8	63	>99	18.3
5	N(CH₃)₄Br	6	64	99	16.8
6		6	64	98	14.6
7	CTAB	6	64	60	3.5
8	KCl	6	11	0
9		6	15	10	4.0

Table 2 Oxidation kinetic resolution of α-methyl benzyl alcohol over complex 1 with various additivesa

Entry	Additive	Additive amount(%)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1			16	0
2	KBr	4	55	69	7.2
3	KBr	6	63	>99	18.3
4	KBr	8	63	>99	18.3
5	N(CH₃)₄Br	6	64	99	16.8
6		6	64	98	14.6
7	CTAB	6	64	60	3.5
8	KCl	6	11	0
9		6	15	10	4.0

Table 3 Oxidation kinetic resolution of α-methyl benzyl alcohol over the complex 1 in different solventa

Entry	Solvent(Volume/mL)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1	H₂O(1.5)	51	70	10.5
2	CH₂Cl₂(1.5)	21	8	2.0
3	H₂O/CH₂Cl₂(1/0.5)	63	>99	18.3
4	H₂O/n-C₆H₁₄(1/0.5)	41	34	4.0
5	H₂O/CH₃CN(1/0.5)	61	52	3.2
6	H₂O/CH₃COOCH₂CH₃(1/0.5)	58	85	11.0
7	H₂O/CH₃COCH₃(1/0.5)	65	67	4.0

Table 3 Oxidation kinetic resolution of α-methyl benzyl alcohol over the complex 1 in different solventa

Entry	Solvent(Volume/mL)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1	H₂O(1.5)	51	70	10.5
2	CH₂Cl₂(1.5)	21	8	2.0
3	H₂O/CH₂Cl₂(1/0.5)	63	>99	18.3
4	H₂O/n-C₆H₁₄(1/0.5)	41	34	4.0
5	H₂O/CH₃CN(1/0.5)	61	52	3.2
6	H₂O/CH₃COOCH₂CH₃(1/0.5)	58	85	11.0
7	H₂O/CH₃COCH₃(1/0.5)	65	67	4.0

Table 4 Oxidation kinetic resolution of various secondary alcohols over complex 1a

Entry	Conversion^b(%)	e.e.^c(%)	k_rel ^d
1	63	>99	18.3
2	60	28	1.9
3	63	95	12.2
4	33	3	1.3

Table 5 Reusability of complex 1a

Entry	Run times	Conversion^b(%)	e.e.^c(%)	k_rel ^d
1	Fresh	63	>99	18.3
2	2nd	62	98	17.2
3	3rd	62	97	15.5
4	4th	62	91	4.3

Table 6 Oxidation kinetic resolution of α-methyl benzyl alcohol over different IL-functionalized complexesa

Entry	Catalyst	Catalyst loading(%)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1	Neat complex	2	55	40	3.5
2	Complex 1	1	53	52	5.8
3	Complex 1	1.5	55	77	10.0
4	Complex 1	2	54	88	19.9
5	Complex 1	3	54	88	19.9

Table 6 Oxidation kinetic resolution of α-methyl benzyl alcohol over different IL-functionalized complexesa

Entry	Catalyst	Catalyst loading(%)	Conversion^b(%)	e.e.^c(%)	$k rel d$
1	Neat complex	2	55	40	3.5
2	Complex 1	1	53	52	5.8
3	Complex 1	1.5	55	77	10.0
4	Complex 1	2	54	88	19.9
5	Complex 1	3	54	88	19.9

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离子液体功能化手性salen Mn(Ⅲ)配合物不对称催化仲醇氧化动力学拆分反应

Ionic Liquid-functionalized Chiral salen Mn(Ⅲ) Complex for Asymmetric Oxidative Kinetic Resolution of Racemic Secondary Alcohols^†

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离子液体功能化手性salen Mn(Ⅲ)配合物不对称催化仲醇氧化动力学拆分反应

Ionic Liquid-functionalized Chiral salen Mn(Ⅲ) Complex for Asymmetric Oxidative Kinetic Resolution of Racemic Secondary Alcohols†

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Ionic Liquid-functionalized Chiral salen Mn(Ⅲ) Complex for Asymmetric Oxidative Kinetic Resolution of Racemic Secondary Alcohols^†