手性胺修饰的羟基磷灰石负载RuCl<sub>2</sub>(TPP)<sub>3</sub>催化不对称氢化苯乙酮

引用本文: 张定林, 杨朝芬, 孙亚萍, 付海燕, 李瑞祥, 陈华, 李贤均. 手性胺修饰的羟基磷灰石负载RuCl₂(TPP)₃催化不对称氢化苯乙酮[J]. 物理化学学报, 2010, 26(10): 2711-2718. doi: 10.3866/PKU.WHXB20101017 shu

Citation: ZHANG Ding-Lin, YANG Chao-Fen, SUN Ya-Ping, FU Hai-Yan, LI Rui-Xiang, CHEN Hua, LI Xian-Jun. Asymmetric Hydrogenation of Acetophenone Catalyzed by RuCl₂(TPP)₃ Supported on Hydroxyapatite Modified with Chiral Amine[J]. Acta Physico-Chimica Sinica, 2010, 26(10): 2711-2718. doi: 10.3866/PKU.WHXB20101017 shu

手性胺修饰的羟基磷灰石负载RuCl₂(TPP)₃催化不对称氢化苯乙酮

摘要:

采用共沉淀法制备了手性胺(L-脯氨酸、D-脯氨酸、(1R,2R)-1,2 -二苯基乙二胺二磺酸钠((1R,2R)-DPENDS) 、(1S,2S)-1,2 -二苯基乙二胺二磺酸钠((1S,2S)-DPENDS)) 修饰的羟基磷灰石(HAP). 并采用傅里叶变换红外(FT-IR) 光谱, 扫描电子显微镜(SEM),X 射线衍射(XRD) 和比表面积测定(BET) 等仪器分析手段对其进行表征. 以手性胺修饰的羟基磷灰石做载体负载RuCl₂(TPP)₃ 催化苯乙酮不对称加氢反应, 详细考察温度、压力、碱的浓度、手性胺负载量等条件对催化反应的影响. 在氢气压力为5.0 MPa 、30 ^oC条件下反应4 h, 苯乙酮的不对称加氢反应, 可获得99.9% 转化率和77.8% 对映选择性, 其结果优于对应的均相催化反应. 实验结果证明, 催化反应在载体表面完成, 催化剂通过简单离心分离可循环使用.

关键词:

English

Asymmetric Hydrogenation of Acetophenone Catalyzed by RuCl₂(TPP)₃ Supported on Hydroxyapatite Modified with Chiral Amine

1.
1. Key Laboratory of Green Chemistry and Technology, Ministry of Education, Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China;
2. Department of Chemistry, School of Pharmacy,The Third Military Medical University, Chongqing 400038, P. R. China
Received Date: 22 April 2010
Available Online: 27 September 2010

Abstract:

Chiral amine (L-proline,D-proline, (1R,2R)-1,2 -diphenyl -1,2 -ethylene diamine sulfonate disodium ((1R, 2R)-DPENDS) and (1S,2S)-1,2 -diphenyl -1,2 -ethylene diamine sulfonate disodium ((1S,2S)-DPENDS)) modified hydroxyapatite (HAP) were prepared and characterized by Fourier transform infrared (FT -IR) spectrometry, scanning electron microscopy (SEM),X-ray diffraction (XRD), and Brunauer -Emmett -Teller (BET) surface area analysis. RuCl₂ (TPP)₃was supported on(1R,2R)-DPENDS modified HAP for the asymmetric hydrogenation of acetophenone. A detailed investigation about the effects of temperature, amount of alkali,H₂ pressure, and concentration of DPENDS modified HAP on the activity and enantioselectivity of acetophenone hydrogenation was undertaken. Under the optimum reaction conditions of 30 ^oC, p(H₂)=5.0 MPa, reaction time of 4 h, the conversion and enantioselectivity reached 99.9% and 77.8% enantiomeric excess (ee), respectively. The results indicated that the asymmetric hydrogenation was accomplished on the surface of the chiral amine modified HAP. The immobilized catalyst was separated from the products by simple centrifugation and reused without adding any other reagents.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

手性胺修饰的羟基磷灰石负载RuCl₂(TPP)₃催化不对称氢化苯乙酮

English

Asymmetric Hydrogenation of Acetophenone Catalyzed by RuCl₂(TPP)₃ Supported on Hydroxyapatite Modified with Chiral Amine

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

手性胺修饰的羟基磷灰石负载RuCl2(TPP)3催化不对称氢化苯乙酮

English

Asymmetric Hydrogenation of Acetophenone Catalyzed by RuCl2(TPP)3 Supported on Hydroxyapatite Modified with Chiral Amine

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

手性胺修饰的羟基磷灰石负载RuCl₂(TPP)₃催化不对称氢化苯乙酮

Asymmetric Hydrogenation of Acetophenone Catalyzed by RuCl₂(TPP)₃ Supported on Hydroxyapatite Modified with Chiral Amine

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs