手性菲咯啉配体促进的铁催化的分子内不对称C(sp^(3))-H键胺化反应  

Chiral Phenanthroline Ligand-Promoted Iron-Catalyzed Enantioselective Intramolecular C(sp^(3))-H Amination

作　　者：李健 鲍蓉蓉 杨雪艳[1] 岑守义 张志鹏 LI Jian;BAO Rongrong;YANG Xueyan;CEN Shouyi;ZHANG Zhipeng(School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化学与分子工程学院,上海200237

出　　处：《华东理工大学学报（自然科学版）》2024年第4期524-533,共10页Journal of East China University of Science and Technology

基　　金：国家自然科学基金(21702059);上海市浦江人才计划(18PJ1402200);中央高校基本科研业务费专项资金(222201717003,JKVJ1231010)。

摘　　要：手性咪唑烷酮类化合物是生物活性分子中一类重要的含氮杂环衍生物,可以转化成具有重要价值的手性1,2-二胺,发展手性含氮杂环化合物的不对称催化合成方法在药物研发中具有重要意义。本文以丰产过渡金属铁为催化剂,以手性氨基酸衍生的菲咯啉为配体,通过分子内1,5-氢迁移实现了N-苯甲酰氧基脲类衍生物的不对称C(sp^(3))-H键胺化反应,以中等至良好的收率(高达68%)和对映体比率(高达81:19)合成了一系列手性咪唑烷酮衍生物。这是极少数已知的利用非酶类铁催化剂实现的不对称C(sp^(3))-H键胺化反应之一。Chiral imidazolidin-2-ones are a kind of important N-heterocycles in bioactive molecules and can be converted to valuable chiral vicinal diamines.It is of great significance to develop catalytic asymmetric transformations for the synthesis of chiral N-heterocycles which play a significant role in drug development.Herein,an asymmetric intramolecular C(sp^(3))-H amination of N-benzoyloxyurea via 1,5-hydrogen atom transfer(HAT)is developed by using earth-abundant iron as the catalyst and chiral amino-acid derived phenanthroline as ligand,affording a series of chiral imidazolidinones in moderate-to-good yields(up to 68%)and enantiomeric ratios(up to 81:19).It is worth noting that this is one of the very few examples of iron-catalyzed enantioselective intramolecular C(sp^(3))-H aminations realized with a nonenzymatic catalyst.

关 键 词：菲咯啉 铁催化 C-H键胺化 咪唑烷酮 对映选择性 

分 类 号：O621.3[理学—有机化学]