Preparation of Axially Grafted Temperature-Responsive Chiral Salen MnIII and Application in Asymmetric Epoxidation of Olefins in Water

doi:10.6023/cjoc202206026

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (1): 244-253.DOI: 10.6023/cjoc202206026 Previous Articles Next Articles

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轴向嫁接型温度响应性手性salen Mn^III聚合物的制备及在纯水相烯烃不对称环氧化反应中的应用

韩彪^a^,^b, 张瑶瑶^a^,^*(), 陈舒晗^a^,^b, 赵梦鸽^a, 李楠^a, 李维双^a, 朱磊^a^,^*()

a 湖北工程学院化学与材料科学学院湖北孝感 432000
b 湖北大学材料科学与工程学院武汉 430062

收稿日期:2022-06-16 修回日期:2022-08-01 发布日期:2022-08-25
通讯作者: 张瑶瑶, 朱磊
基金资助:
湖北省教育厅中青年人才(Q20212704); 国家自然科学基金(22108065); 国家自然科学基金(21774029)

Preparation of Axially Grafted Temperature-Responsive Chiral Salen Mn^III and Application in Asymmetric Epoxidation of Olefins in Water

Biao Han^a^,^b, Yaoyao Zhang^a(), Shuhan Chen^a^,^b, Mengge Zhao^a, Nan Li^a, Weishuang Li^a, Lei Zhu^a()

a School of Chemistry and Materials Science, Hubei Engineering University, Xiaogan, Hubei 432000
b School of Materials Science and Engineering, Hubei University, Wuhan 430062

Received:2022-06-16 Revised:2022-08-01 Published:2022-08-25
Contact: Yaoyao Zhang, Lei Zhu
Supported by:
Hubei Provincial Education Department Youth and Middle-Aged Talents Project(Q20212704); National Natural Science Foundation of China(22108065); National Natural Science Foundation of China(21774029)

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Abstract

A series of temperature-responsive polymers (poly N-isopropylacrylamide-co-N,N-dimethylacrylamide, PN_xD_y) were prepared by using N-isopropylacrylamide (NIPAAm) and N,N-dimethylacrylamide (DMAM) as reaction monomers, azobisisobutyronitrile as chain initiator, and mercaptoethylamine hydrochlorides as chain transfer agents. Then, a novel thermoresponsive surfactant-type chiral salen Mn^III catalyst PN_xD_yMn was developed by axially grafting “smart” polymer (PN_xD_y) onto the metal center of a neat chiral salen Mn^III complex. The temperature-sensitivity, structure and morphology of the polymers were studied through a series of characterizations, and it was found that these temperature-responsive chiral polymers can efficiently catalyze the asymmetric epoxidation of olefins in pure water. Only 0.5 mol% PN₇₅D₅Mn was sufficient to exhibit extremely high activity (conversion>99%) with up to 76% enantioselectivity and turnover frequency (TOF) (396/h) for a substrate of indene in water. The conversion rate of the substrate styrene was as high as 99% in 5 min, and the TOF value reached 2376/h. Characterization and experiments proved that PN_xD_yMn can self-assemble into nanoreactors for the asymmetric epoxidation of olefin in water, leading to an acceleration of reaction and causing selective effects. After reaction, the PN_xD_yMn exhibited hydrophobic properties upon heating above its lower critical solution temperature (LCST), and precipitated from the aqueous system for recovery. It can be recycled and reused for seven times without significant loss of activity, and no organic solvents were required for the reaction and separation process.

Key words: axial-grafting, temperature-responsive, chiral salen Mn^III complex, asymmetric epoxidation of olefin in water, recycle and reuse

Cite this article

Biao Han, Yaoyao Zhang, Shuhan Chen, Mengge Zhao, Nan Li, Weishuang Li, Lei Zhu. Preparation of Axially Grafted Temperature-Responsive Chiral Salen Mn^III and Application in Asymmetric Epoxidation of Olefins in Water[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 244-253.

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Fig. & Tab. 11

Scheme 1. Preparation of the neat complex chiral salen MnIII catalyst

Scheme 2. Preparation of the thermoresponsive PNxDyMn catalyst Preparation of the thermoresponsive PNxDyMn catalyst

Figure 1. FTIR spectra of (a) PN75D5, (b) fresh PN75D5Mn, (b') PN75D5Mn reused for five times, and (c) neat salen MnIII complex

Figure 2. UV-vis spectra of PN75D5Mn (A) and neat salen MnIII (B) in dichloromethane (a), acetone (b), acetonitrile (c), methanol (d), and water (e)

Figure 3. (A) LCST spectra of PNxDyMn, and (B) temperature response performance curves of PNxDyMn

Figure 4. TEM micrograph of self-folded PN60Mn (a), PN90- D5Mn (b), PN75D5Mn (c), PN60D5Mn (d) and the size distribution of self-folded in water at a concentration of 0.5 mg?mL–1 at room temperature

Figure 5. Critical micelle concentration (CMC) of PN75D5Mn in water at 25 ℃

Entry	Polymer	Solvent	Conv.^b/%	ee^c/%	TOF^d/h^–1
1	Neat salen Mn^III	H₂O	17	38	68
2	Neat salen Mn^III	Dichlormethane	21	43	84
3	PN₇₅D₅	H₂O	—	—	—
4	PN₆₀Mn	H₂O	86	69	344
5	PN₉₀D₅Mn	H₂O	92	72	368
6	PN₇₅D₅Mn	H₂O	99	76	396
7	PN₇₅D₅Mn	Dichlormethane	64	65	256
8	PN₆₀D₅Mn	H₂O	95	73	380
9	PD₆₀Mn	H₂O	56	59	296

Table 1. Asymmetric epoxidation of styrene over different catalysts in water

Entries	Catalyst	t/min	Conv.^b/%	ee^c/%	TOF^d/h^–1
1	PN₇₅D₅Mn	30	99	76	396
2	Neat salen Mn^III	30	17	38	68
3	PN₇₅D₅Mn	5	99	40	2376
4	Neat salen Mn^III	5	21	6	504
5	PN₇₅D₅Mn	25	99	49	475
6	Neat salen Mn^III	25	26	26	125
7	PN₇₅D₅Mn	40	99	79	297
8	Neat salen Mn^III	40	18	48	54
9	PN₇₅D₅Mn	190	99	96	63
10	Neat salen Mn^III	190	39	78	25
11	PN₇₅D₅Mn	180	99	93	66
12	Neat salen Mn^III	180	37	80	25

Table 2. Asymmetric epoxidation of unfunctionalized olefins over PN75D5Mn and neat salen MnIII in water

Figure 6. (A) Reuse of PN75D5Mn in asymmetric epoxidation of indene in water, (B) photograph of PN75D5Mn dissolved in water 25 ℃, and (C) photograph of PN75D5Mn separated from water by raising temperature to 50 ℃

Polymer	x∶y^a	M_w^b	LCST^c	TEM形貌
PN₆₀	60∶0	6348	32.0	粒子
PN₉₀D₅	90∶5	10327	31.0	球状
PN₇₅D₅	75∶5	8930	30.0	棒状
PN₆₀D₅	60∶5	7259	29.0	球状
PD₆₀	0∶60	5921	—	无规

Table 3. Characterization of five polymers with different hydrophilic and hydrophobic ratios

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轴向嫁接型温度响应性手性salen Mn^III聚合物的制备及在纯水相烯烃不对称环氧化反应中的应用

Preparation of Axially Grafted Temperature-Responsive Chiral Salen Mn^III and Application in Asymmetric Epoxidation of Olefins in Water

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