轴向嫁接型温度响应性手性salen MnIII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

doi:10.6023/cjoc202206026

摘要/Abstract

以不同比例的N-异丙基丙烯酰胺(NIPAAm)和N,N-二甲基丙烯酰胺(DMAM)为反应单体, 偶氮二异丁腈为链引发剂, 巯基乙胺盐酸盐为链转移剂, 制备出一系列温度响应性聚合物(聚N-异丙基丙烯酰胺-co-N,N-二甲基丙烯酰胺, PN_xD_y). 再与传统手性salen Mn^III配合物进行轴向嫁接, 得到多种形貌轴向嫁接型温度响应性手性salen Mn^III聚合物PN_xD_yMn. 通过系列表征研究聚合物的温敏性、结构以及形貌, 并发现该类温度响应性手性聚合物在纯水相中, 能高效催化烯烃不对称环氧化反应的进行, 仅需0.5 mol% PN₇₅D₅Mn催化反应30 min, 即可以99%的收率、76%的对映选择性实现底物茚的转化, 转换频率(TOF)值高达396/h. 底物苯乙烯5 min转化率高达99%, TOF值为2376/h. 结合表征和实验, 证明PN_xD_yMn在水中可自组装形成纳米反应器, 限域效应加速了反应进行. 反应结束后, 升温至最低临界温度(LCST)以上, PN_xD_yMn表现出疏水特性, 从水相析出后回收并进行重复使用, 反应与分离过程中无需使用任何有机溶剂.

关键词: 轴向嫁接, 温度响应性, 手性salen Mn^III配合物, 水相烯烃不对称环氧化, 回收及重复使用

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

引用此文

韩彪, 张瑶瑶, 陈舒晗, 赵梦鸽, 李楠, 李维双, 朱磊. 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[J]. 有机化学, 2023, 43(1): 244-253.

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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图/表 11

图式1. 传统手性salen MnIII的制备流程图

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

图式2. 温敏催化剂PNxDyMn的制备流程图

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

图1. (a) PN75D5、(b)新制备催化剂PN75D5Mn、(b')循环五次回收后催化剂PN75D5Mn以及(c)传统salen MnIII催化剂的红外表征

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

图2. 温敏催化剂PN75D5Mn (A)和传统salen MnIII (B)在CH2Cl2 (a)、丙酮(b)、乙腈(c)、甲醇(d)、水(e)中的紫外图

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)

图3. (A) PNxDyMn的LCST表征和(B) PNxDyMn的温度响应性表征

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

图4. 聚合物PN60Mn (a), PN90D5Mn (b), PN75D5Mn (c), PN60D5Mn (d)在室温条件下浓度为0.5 mg?mL–1的水溶液中自折叠行为的TEM表征以及动态光散射图

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

图5. 温敏催化剂PN75D5Mn在水中, 25 ℃条件下的临界胶束浓度(CMC)表征

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

表1. 不同催化剂应用于纯水相茚的不对称环氧化反应中a

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

表2. PN75D5Mn和传统salen MnIII应用于纯水相中非官能团化烯烃不对称环氧化反应a

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

图6. (A) PN75D5Mn在茚的不对称环氧化反应中回收性能考查、(B)催化剂PN75D5Mn在25 ℃溶于水和(C)催化剂PN75D5Mn在50 ℃从水中析出

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

表3. 五种不同亲疏水比例聚合物的表征性能

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

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