Experimental and mechanistic insights into copper(II)-dioxygen catalyzed oxidative N-dealkylation of N-(2-pyridylmethyl)phenylamine and its derivatives

被引：9

作者：

Wang, Yang ^{[1
]}

Liu, Haixiong ^{[1
]}

Zhang, Xiaofeng ^{[1
]}

Zhang, Zilong ^{[1
]}

Huang, Deguang ^{[1
]}

机构：

[1] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2017年 / 15卷 / 43期

基金：

中国国家自然科学基金;

关键词：

COPPER-DIOXYGEN REACTIVITY; C-H; SUBSTRATE HYDROXYLATION; BOND ACTIVATION; COMPLEX; AMINES; MONOOXYGENASE; CHEMISTRY; PROTEINS; OXYGENATION;

D O I：

10.1039/c7ob02192e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A di-(2-pyridylmethyl) phenylamine ((PyCH2)(2)NPh) supported Cu(II)/O-2 catalytic system was explored with the synthesis of pyridylmethyl-based compounds of carboxylate (PyCOOH), amide (PyC(O)NHPh), and imine (PyCH=NPh) from the oxidative N-dealkylation of N-(2-pyridylmethyl) phenylamine (PyCH2NHPh) and its derivatives, by means of controlling the addition of a base and/or water to the reaction system under a dioxygen atmosphere at room temperature. Experimental studies showed that the imine and amide species could be precursors in succession in the way to the final oxidation state of carboxylates. A cyclic catalytic mechanism was proposed including the base triggered C-H bond activation of the 2-pyridylmethyl group (PyCH2-) and the intermolecular Cu-OOH alpha-hydrogen atom abstraction from the coordinated imine substrate (PyCH=NPh).

引用

页码：9164 / 9168

页数：5

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