A Highly Versatile Catalyst System for the Cross-Coupling of Aryl Chlorides and Amines
A Highly Versatile Catalyst System for the Cross-Coupling of Aryl Chlorides and Amines
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DOI：
10.1002/chem.200902316
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Stradiotto, Mark
中科院分区：
文献类型：
--
作者：
Lundgren, Rylan J.;Sappong-Kumankumah, Antonia;Stradiotto, Mark
报道了2-（二叔丁基膦基）-N，N-二甲基苯胺（L1，71%）和2-（二-1-金刚烷基膦基）-N，N-二甲基苯胺（L2，74%）的合成及其在Buchwald-Hartwig胺化反应中的应用。与[Pd（烯丙基）Cl]（2）或[Pd-Cl]（2）组合，（肉桂基）Cl]（2）这些结构简单且空气稳定的P，N配体使得芳基和杂芳基氯化物，包括带有可烯醇化的酮、醚、酯、羧酸、酚、醇、烯烃、酰胺和卤素作为取代基的那些能够交叉偶联到各种胺和相关底物，包括伯烷基和芳基胺，环状和非环状仲胺、N-H胺、腙、氨基锂和氨。在许多情况下，反应可以在低催化剂负载量（0.5-0.02摩尔% Pd）下进行，具有优异的官能团耐受性和化学选择性。还报道了涉及1，4-溴氯苯和碘苯的交叉偶联反应的实例。在相似的条件下。当使用Pd（OAc）（2）、PdCl 2 [PdCl 2（cod）]时，获得较差的催化性能（cod = 1，5-环辛烷）、[PdCl 2（MeCN）（2）]或[Pd-2（dba）（3）]（dba =二亚苄基丙酮）与L1或L2的组合，或通过使用[Pd（烯丙基）Cl]（2）或[Pd（肉桂基）Cl]（2），其中L1和L2的变体在磷上具有较低碱性或较低空间要求的取代基或缺乏邻-二甲基氨基片段。考虑到与已建立的配体类别相关的关于在C-N偶联应用的多种可能范围内保持高活性的当前限制，L1和L2代表用于芳基氯和交叉偶联胺的异常通用的配体系统。
The syntheses of 2-(di-tert-butylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamatylphosphino)-N,N-dimethylaniline (L2, 74%), and their application in Buchwald-Hartwig amination, are reported. In combination with [Pd(allyl)Cl](2) or [Pd-(cinnamyl)Cl](2) these structurally simple and air-stable P,N ligands enable the cross-coupling of aryl and heteroaryl chlorides, including those bearing as substituents enolizable ketones, ethers, esters, carboxylic acids, phenols, alcohols, olefins, amides, and halogens, to a diverse range of amine and related substrates that includes primary alkyl- and arylamines, cyclic and acyclic secondary amines, N-H amines, hydrazones, lithium amide, and ammonia. In many cases, the reactions can be performed at low catalyst loadings (0.5-0.02 mol% Pd) with excellent functional group tolerance and chemoselectivity. Examples Of cross-coupling reactions involving 1,4-bromochlorobenzene and iodobenzene are also reported. Under similar conditions. inferior catalytic performance was achieved when using Pd(OAc)(2), PdCl2 [PdCl2(cod)] (cod = 1,5-cyclooctadiene), [PdCl2(MeCN)(2)], or [Pd-2(dba)(3)] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(ally])Cl](2) or [Pd(cinnamyl)Cl](2), with variants of L1 and L2 bearing less basic or less sterically demanding substituents on phosphorus or lacking an ortho-dimethylamino fragment. Given Current limitations associated with established ligand classes with regard to maintaining high activity across the diverse possible range of C-N Coupling applications, L1 and L2 represent unusually versatile ligand systems for the Of aryl chlorides and cross-coupling amines.