Amination and Etherification of Aryl Halides and Olefins

芳基卤化物和烯烃的胺化和醚化

基本信息

批准号：
7344788
负责人：
John F Hartwig
金额：
$ 30.57万
依托单位：
UNIVERSITY OF ILLINOIS AT URBANA-CHAMPAIGN
依托单位国家：
美国
项目类别：
财政年份：
1999
资助国家：
美国
起止时间：
1999-02-01 至 2009-01-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/7344788
关键词：
Alkenes Amides Amination Amines Amino Acids Amino Alcohols Aniline Anions Aromatic Amines Behavior Binding Biological Chemistry Chloride Ion Chlorides Class Complex Condition Coupling Data Dependence Development Dissociation Eating Equilibrium Esters Ethers Ethyl Ether Grant Halogens Heterocyclic Amines Imides Imines Investigation Kinetics Lanthanoid Series Elements Life Ligands Methods Mono-S Nitrogen Object Attachment Palladium Phosphines Poison Process Property Publishing Rate Reaction Reagent Relative (related person)Request for Applications Research Rest Ruthenium Series Shapes Solutions Solvents Structure Sulfonamides System Time Transition Elements Universities Work Zinc base catalyst diene epimerization functional group improved metal complex phosphine programs reaction rate research study simulation stereochemistry unpublished works

项目摘要

DESCRIPTION (provided by applicant): This research program encompasses palladium-catalyzed amination and etherification of aryl halides and palladium-catalyzed hydroamination of olefins. Studies during the previous grant period led to some of the most active catalysts for the palladium-catalyzed amination and etherification, including three different catalysts sold or used commercially. In unpublished work, we have isolated the true amido and alkoxo intermediates in reactions with the most active catalysts and have gained initial results that suggest a solution to the amination and etherification of heteroaromatic substrates, which typically poison or retard the activity of the most active palladium catalysts for aryl amination. We have also found palladium catalysts for the hydroamination of dienes and vinylarenes with both aromatic and aliphatic amines and have found conditions for highly enantioselective hydroamination of dienes. We have uncovered the mechanism for palladium-catalyzed hydroamination and have isolated the intermediate that reacts with amine to form the hydroamination product. Most recently, we discovered the first hydroamination of olefins catalyzed by ruthenium complexes, and the scope of the proposed research will expand to include these new catalysts for hydroamination. This application requests renewed support for studies of recently developed catalysts for each of these reactions. We will investigate the mechanisms of catalytic amination and etherification of aryl chlorides and tosylates. These investigations will include studies to reveal the chemistry of new three-coordinate amido and alkoxo complexes and studies to unravel the complex kinetic behavior that results from a dependence of the reaction rate on the concentration of base and halogen. In addition, we will investigate reactions with ligands based on a chelating structure with hindered dialkylphosphino substituents that will increase the scope of the couplings and should increase the lifetimes of the catalysts. The structure of this ligand generates palladium complexes that undergo fast oxidative addition but resist displacement by amines or basic heterocycles. In addition, we will investigate the scope and mechanism of the hydroamination reactions we have discovered. We will investigate the effects of varying ligand structure on the rates and selectivities of the palladium-catalyzed hydroamination of vinylarenes and will delineate the basic steps of the ruthenium-catalyzed reactions. With recently identified palladium catalysts that display higher activities than those of the original systems, we will investigate the functional group tolerance of the reactions catalyzed by these complexes. In addition, we will strive to develop conditions to add other nitrogen substrates to vinylarenes and to add amines to more substituted vinylarenes and simple alkenes.

描述（由申请人提供）：该研究计划包括钯催化的胺化和芳基卤化物和钯催化的烯基盐水的醚化。在上一个赠款期间的研究导致了钯催化的胺化和以太化的一些最活跃的催化剂，包括三种不同的催化剂出售或商业使用。在未发表的工作中，我们已经在与最活跃的催化剂的反应中分离了真实的amido和arkoxo中间体，并获得了最初的结果，这些结果表明解决了异芳基底物的胺化和醚化，通常会毒化或阻碍最活跃的钯的活性用于芳基胺化的催化剂。我们还发现了钯催化剂，用于具有芳族和脂肪胺的二烯和乙烯基烯二烯和乙烯基烯，并且发现了高度对映射二烯的启示式选择性氢化的条件。我们发现了钯催化氢化的机制，并分离了与胺反应形成氢化产物的中间体。最近，我们发现了由芳族复合物催化的烯烃的第一次盐水，并且拟议的研究范围将扩大，以包括这些新的水域催化剂。该应用程序要求为每种反应的最近开发的催化剂进行研究，以重新支持研究。我们将研究芳基氯化物和甲苯二甲酸酯的催化胺化和醚化的机制。这些研究将包括研究揭示新的三坐标胺和烷氧化型复合物的化学性质以及研究，以揭示复杂的动力学行为，这是由于反应速率依赖于碱和卤素浓度的依赖性而产生的。此外，我们将基于螯合结构与螯合结构的配体进行反应，以阻碍的二烷基磷酸取代基，这将增加耦合的范围，并应增加催化剂的寿命。该配体的结构产生钯络合物，可快速氧化添加，但抗胺或碱性杂环的位移。此外，我们将研究我们发现的水域反应的范围和机制。我们将研究不同配体结构对乙烯基烯烃的钯催化氢化疗法的速率和选择性的影响，并将描述氟苯甲状腺催化反应的基本步骤。随着最近发现的钯催化剂显示出比原始系统的活性更高的活性，我们将研究这些复合物催化的反应的功能群耐受性。此外，我们将努力开发条件，将其他氮底物添加到乙烯基烯烃中，并将胺添加到更多取代的乙烯基烯烃和简单的烯烃中。