Synthesis of Amine Functionalized ZPS-PVPA Supported Chiral MnⅢ(salen) and Asymmetric Catalytic Olefin Epoxidation†

doi:10.7503/cjcu20190011

Abstract

Abstract:

Using zirconium poly(styrene-phenylvinyl-phosphonate)-phosphate(ZPS-PVPA) as a catalyst carrier, the hydroxyl group in the inorganic zirconium hydrogen phosphate was modified by 3-aminopropyltrimethoxysilane. Then, the chiral Mn^Ⅲ(salen) was axially immobilized onto amine functionalized ZPS-PVPA. The immobilized catalyst were characterized by FTIR, DR UV-Vis, AAS, SEM, TEM, XPS, X-ray and EDS. The successful preparation of heterogeneous catalysts was confirmed. Subsequently, the catalytic performance of the supported catalyst for α-methylstyrene, styrene and indene was examined in detail. The results showed that the reaction was carried out at 0 ℃ for 3 h, the amount of catalyst was 0.03 mmol, the e. e. value was 91.5% with a 99% conversion when α-methylstyrene was investigated using m-chloroperoxybenzoic acid as oxidant and in the present of the axial ligand N-methylmorpholine nitrogen oxide(NMO). In addition, the recycling performance of the catalyst was examined using indene as a substrate. After 10 times of repeated use of the catalyst, the e. e. values(>90%)are significantly better than those achieved under a homogeneous counterparts(e. e. 65%).

Key words: Zirconium poly(styrene-phenylvinyl-phosphonate)-phosphate, 3-Aminopropyltrimethoxysilane, Chiral Mn^Ⅲ(salen) catalyst, Asymmetric epoxidation

CLC Number:

O643.3

TrendMD:

ZOU Xiaochuan,WANG Yue,WANG Cun,HU Shiwen,SHI Kaiyun. Synthesis of Amine Functionalized ZPS-PVPA Supported Chiral Mn^Ⅲ(salen) and Asymmetric Catalytic Olefin Epoxidation^†[J]. Chem. J. Chinese Universities, 2019, 40(7): 1488.

Figures/Tables 7

Scheme 1 Synthetic route of the immobilized catalyst 1

Fig.1 IR spectra(A), UV-Vis spectra(B) of MnⅢ(salen)(a) and the immobilized catalyst 1(b) and XPS spectrum of the immobilized catalyst 1(C)

Fig.2 SEM images of ZPS-PVPA(A) and the immobilized catalyst 1(B), TEM image of the immobilized catalyst 1(C) and the measured EDS image of ZPS-PVPA(D) and the immobilized catalyst 1(E)

Fig.3 EDS elementary mapping of layered image of the immobilized catalyst 1(A), elements C(B), O(C), P(D), Si(E) and Mn(F) in the immobilized catalyst 1

Fig.4 XRD patterns of ZAPS-PVPA(a) and the immobilized catalyst 1(b)

Table 1 Asymmetric epoxidation of different substrates by catalyzed MnⅢ(salen) and heterogeneous catalyst 1a

Entry	Catalyst	Oxidant	Time/h	Conversion^b(%)	Selectivity^b(%)	e. e.^c(%)
1	Mn^Ⅲ(salen)	m-CPBA/NMO	1	99.9	99.1	52.0^d
2	Catalyst 1	m-CPBA/NMO	3	>99	87.6	91.5^d
3	Catalyst 1	m-CPBA	3	71.6	74.3	12.1^d
4	Mn^Ⅲ(salen)	m-CPBA/NMO	1	99.9	98.7	46.2^d
5	Catalyst 1	m-CPBA/NMO	3	95.1	99.1	63.9^d
6	Catalyst 1	m-CPBA	3	69.6	81.7	3.90^d
7	Mn^Ⅲ(salen)	m-CPBA/NMO	1	99.9	99.8	65.0^e
8	Catalyst 1	m-CPBA/NMO	3	>99	>99	>99^e
9	Catalyst 1	m-CPBA	3	80.5	85.6	11.8^e

Table 2 Recycles of immobilized catalyst 1 in the epoxidation of indenea

Run	Time/h	Conversion^b(%)	Selectivity^b(%)	e. e.^c(%)
1	3	>99	>99	>99^d
2	3	99.1	>99	>99^d
3	3	99.0	97.3	98.1^d
4	3	98.7	96.1	97.9^d
5	3	98.0	92.6	95.6^d
6	3	97.6	90.0	94.9^d
7	3	96.8	88.2	93.2^d
8	3	96.1	85.6	92.6^d
9	3	92.7	83.1	91.3^d
10	3	87.4	79.9	90.1^d
11	3	96.2	89.3	94.2^d
12	3	96.1	88.8	93.5^d

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