A3B型卟啉合成方法及在仿生催化中的应用  

Synthesis of A_3B-type meso-substituted unsymmetrical porphyrins and their application in biomimetic catalysis

作　　者：佘远斌[1,2] 李凯[1] 王朝明[1] 于艳敏[1] 

机构地区：[1]北京工业大学环境与能源工程学院绿色化学与精细化工研究所,北京100124 [2]中南民族大学化学与材料科学学院催化材料科学国家民委一教育部共建暨湖北省重点实验室,湖北武汉430074

出　　处：《化工进展》2014年第6期1444-1452,共9页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(21276006、21036009);科技部科技支撑(攻关)计划(2009BAK61B00)项目

摘　　要：作为金属卟啉类化合物的一个重要类别,A3B型卟啉化合物具有独特的物理、化学、光电及结构特性。本文综述了国内外有关该类化合物的合成方法及在仿生催化应用领域的最新研究成果,系统地介绍了混醛法(Little法和Lindsey法)、"2+2"合成法、线性四烷基吡咯合成法、卟啉中位修饰法和微波合成法。重点阐述了具有独特结构的A3B型卟啉类仿生催化剂——B-链衍生化催化剂、固载A3B型金属卟啉催化剂、A3B型金属卟啉二聚体催化剂、Pacman型双核金属卟啉催化剂及Hangman型金属卟啉催化剂在仿生催化领域中的应用,希望能为卟啉研究者设计、合成更优良的卟啉类催化剂提供参考。未来卟啉仿生催化的主要目标在于合成性能更加优良的卟啉,并应用于大规模工业生产中,在温和条件下实现较高的转化数和选择性。As an important branch of porphyrin compounds,A3B-type meso-substituted unsymmetrical porphyrins have extraordinarily and remarkably diverse physical,chemical,photoelectrical and structural properties. The synthesis methods of A3B-type meso-substituted unsymmetrical porphyrins are discussed,involving the mixed aldehyde method,the“2＋2”route,the bilane route,the derivation of porphyrin route and the microwave radiation method. Accordingly,some applications of various A3B-type meso-substituted unsymmetrical porphyrins as biomimetic catalysts are elaborated. These porphyrins and their derivatives are designed,such as B-derived porphyrins which connect with other units of specific functions through the distinct meso-substituted chain , supported A3B-metalloporphyrins,A3B-metalloporphyrins dimer,Pacman bis-metalloporphyrin constructs and Hangman metalloporphyrin constructs. The future main objective of porphyrin biomimetic catalytic is to synthesize more excellent porphyrins and be used in large-scale industrial production,achieving higher enantioselectivity and larger turn-over number under mild conditions.

关 键 词：A3B型卟啉 合成 催化 氧化 

分 类 号：O641.4[理学—物理化学] O643.3[理学—化学]