钯催化六氢三嗪烯基化合成二级烯丙胺  

Palladium-catalyzed vinylation of triazinanes for the synthesis of secondary allylamines

作　　者：丁永正 李加文 黄汉民 DING Yong-zheng;LI Jia-wen;HUANG Han-min(Hefei National Laboratory for Physical Sciences at the Microscale,School of Chemistry and Materials Science,University of Science and Technology of China,Hefei 230026,China;State Key Laboratory for Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China)

机构地区：[1]中国科学技术大学化学与材料科学学院合肥微尺度物质科学国家研究中心,合肥230026 [2]中国科学院兰州化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

出　　处：《分子科学学报》2021年第1期77-84,共8页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(21925111,21672199,21790333,21702197)。

摘　　要：本文报道了一种利用简单烯烃和六氢三嗪为原料,钯催化六氢三嗪烯基化合成二级烯丙胺的方法.该反应区域选择性高,反应条件简单,能一步以中等以上的收率得到一系列线性的E-型N-芳基取代二级烯丙胺.Allylamine is an important structural unit which is widely exist in natural products and pharmaceutical molecules with biological activity.Meanwhile,allylamine is also an important synthetic building block in many synthetic transformations.In view of its importance in organic and medicinal chemistry,many methods for synthesizing allylamines have been developed.Amongthese methods,the use of allyl compounds via formation ofπ-allyl metal intermediates to synthesize allylamine is the most common strategy.However,the required pre-preparation of activated allyl compounds in advance,and the produce of stoichiometric by-products during the preparation of these compounds and the amination reaction significantly decrease the step economy and atom economy of the whole process.Therefore,it is of great significance to develop a novel and efficient method for the synthesis of allylamines.In 2012,our group has reported a new type of palladium-catalyzed olefin aminomethylation reaction for the first time.This reaction uses simple olefins and easily available aminals as starting materials,and can obtain a series of linear E-type allylamine compounds with high regioselectivities and high yields.Mechanistic studies have shown that a new cyclopalladated complex was formed via oxidative addition of Pd(0)to aminal,which is now known as Huang-Complex.Based on this study,our group developed a series of new reactions that employed Huang-Complex as a leading-complex,and applied them to the synthesis of a series of nitrogen-containing compounds.However,these methods can only synthesize N-alkyl substituted tertiary allylamines,and cannot obtain Naryl substituted allylamines or secondary allylamines.Herein,we report a new palladium-catalyzed aminomethylation of olefins for the direct synthesis of N-aryl secondary allylamine compounds by using triazinanes as an alternative to aminals.This reaction uses olefins and N-aryltriazinanes as starting materials,1,4-dioxane as solvent,and Pd(Xant-phos)(CH3 CN)2(OTf)2 as the catalyst.This protocol can

关 键 词：钯催化剂 六氢三嗪 烯烃 烯丙胺 

分 类 号：O621[理学—有机化学]