手性双提蓝钴卟啉配合物催化二氧化碳对环氧的不对称环加成

doi:10.1016/S1872-2067(18)63023-2

催化学报 ›› 2018, Vol. 39 ›› Issue (5): 997-1003.DOI: 10.1016/S1872-2067(18)63023-2

手性双提蓝钴卟啉配合物催化二氧化碳对环氧的不对称环加成

付西英^a, 景心瑶^a, 靳丽丽^b, 张立龙^a, 张晓峰^a, 胡斌^c, 景欢旺^a,d

a 兰州大学化学化工学院功能有机分子化学国家重点实验室, 甘肃兰州 730000;
b 中国药科大学理学院, 江苏南京 210009;
c 中国科学院兰州学物理研究所羰基合成与选择氧化国家重点实验室, 甘肃兰州 730000;
d 中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001

收稿日期:2017-12-06 修回日期:2017-12-27 出版日期:2018-05-18 发布日期:2018-04-19
通讯作者: 景欢旺
基金资助:
国家自然科学基金（21173106，20973086）；甘肃省自然科学基金（17JR5RA212）；煤转化国家重点实验室开放基金（J17-18-913-2）.

Chiral basket-handle porphyrin-Co complexes for the catalyzed asymmetric cycloaddition of CO₂ to epoxides

Xiying Fu^a, Xinyao Jing^a, Lili Jin^b, Lilong Zhang^a, Xiaofeng Zhang^a, Bin Hu^c, Huanwang Jing^a,d

a State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China;
b College of Sciences, China Pharmaceutical University, Nanjing 210009, Jiangsu, China;
c State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China;
d State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China

Received:2017-12-06 Revised:2017-12-27 Online:2018-05-18 Published:2018-04-19
Contact: 10.1016/S1872-2067(18)63023-2
Supported by:
This work was financially supported by the National Natural Science Foundation of China (21173106, 20973086), the Natural Science Foundation of Gansu Province (17JR5RA212), and the Foundation of State Key Laboratory of Coal Conversion (J17-18-913-2).

摘要/Abstract

摘要：

绿色化学是当今化学科学研究的前沿领域.仿生催化是绿色合成技术和方法学研究的一个重要方面.生物质和酶分子在酶催化转化过程中的"构-效"关系可以通过仿生催化进行模拟研究.CO₂作为温室气体的主要成分是造成全球气候变暖的主要因素，但它同时也是C1化学的重要原料.利用CO₂与有机环氧化合物通过偶联反应制备有机环碳酸酯或聚碳酸酯则是CO₂化学研究的热点之一，并已经取得了长足的进步.但是运用手性催化剂对此反应进行不对称环加成得到手性环碳酸酯的研究不多.
本文首次设计并合成了具有双提篮结构的手性钴卟啉螯合物.其中的提篮部分由手性联萘酚（S或R）和L-苯丙氨酸组成，从卟啉骨架的meso位引入，首先制备了两种手性结构的自由卟啉配体（6a，7a）；然后与醋酸钴反应得到两种二价钴卟啉手性配合物（6b，7b），加入醋酸后，通过空气氧化得到三价钴卟啉手性催化剂（6c，7c）.采用紫外、红外光谱、质谱和核磁共振（包括二维NMR）等技术对得到的卟啉中间化合物、配合物和催化剂进行了详细的表征，确定了化合物的结构.将得到的三价钴卟啉配合物作为手性催化剂用于CO₂和环氧化合物的不对称环加成反应.结果表明，提篮的手性基团对小分子的环氧化合物环氧丙烷具有手性选择性，在低温-20℃下，可以得到大于50%的ee值.同时由于提篮与卟啉平面空间的有限性，导致分子体积较大的环氧化合物与CO₂的反应很慢，也没有发现其对环碳酸酯的对映选择性.我们相信本工作对于合成手性卟啉分子及其在不对称催化中的应用具有一定的意义.

关键词: 二氧化碳固定, 手性拆分, 环加成, 环氧化合物, 手性钴卟啉配合物

Abstract:

The catalytic synthesis of cyclic carbonates via the cycloaddition of CO₂ to epoxides is a standard methodology for CO₂ fixation. For this purpose, chiral basket-handle porphyrin-Co complexes were devised, prepared, and fully characterized by nuclear magnetic resonance, mass spectrometry, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and specific rotation. The proposed metalloporphyrin catalysts were synthesized with either 1,1'-bi-2-naphthol or L-phenylalanine, which have different chirality, and then applied to the coupling of propylene oxide and CO₂ for generating chiral cyclic carbonates with good enantioselectivity under extremely mild conditions in the presence of tetrabutyl ammonium chloride as a co-catalyst. The good enantioselectivity in the cycloaddition reaction is attributed to a synergistic interplay between the chiral porphyrin catalysts and the substrate. The mechanism and enantioselectivity of the asymmetric cycloaddition reaction is discussed.

Key words: Carbon dioxide fixation, Chiral resolution, Cycloaddition, Epoxide, Chiral porphyrin-cobalt complex

付西英, 景心瑶, 靳丽丽, 张立龙, 张晓峰, 胡斌, 景欢旺. 手性双提蓝钴卟啉配合物催化二氧化碳对环氧的不对称环加成[J]. 催化学报, 2018, 39(5): 997-1003.

Xiying Fu, Xinyao Jing, Lili Jin, Lilong Zhang, Xiaofeng Zhang, Bin Hu, Huanwang Jing. Chiral basket-handle porphyrin-Co complexes for the catalyzed asymmetric cycloaddition of CO₂ to epoxides[J]. Chinese Journal of Catalysis, 2018, 39(5): 997-1003.

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手性双提蓝钴卟啉配合物催化二氧化碳对环氧的不对称环加成

Chiral basket-handle porphyrin-Co complexes for the catalyzed asymmetric cycloaddition of CO₂ to epoxides

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手性双提蓝钴卟啉配合物催化二氧化碳对环氧的不对称环加成

Chiral basket-handle porphyrin-Co complexes for the catalyzed asymmetric cycloaddition of CO2 to epoxides

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Chiral basket-handle porphyrin-Co complexes for the catalyzed asymmetric cycloaddition of CO₂ to epoxides