86295-20-7Relevant academic research and scientific papers
Formal Direct Cross-Coupling of Phenols with Amines
Chen, Zhengwang,Zeng, Huiying,Girard, Simon A.,Wang, Feng,Chen, Ning,Li, Chao-Jun
supporting information, p. 14487 - 14491 (2016/01/25)
The transition-metal-catalyzed amination of aryl halides has been the most powerful method for the formation of aryl amines over the past decades. Phenols are regarded as ideal alternatives to aryl halides as coupling partners in cross-couplings. An efficient palladium-catalyzed formal cross-coupling of phenols with various amines and anilines has now been developed. A variety of substituted phenols were compatible with the standard reaction conditions. Secondary and tertiary aryl amines could thus be synthesized in moderate to excellent yields.
NOVEL CATALYSTS
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Page/Page column 69, (2012/06/01)
The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.
Rational and predictable chemoselective synthesis of oligoamines via Buchwald-Hartwig amination of (hetero)aryl chlorides employing Mor-Dalphos
Tardiff, Bennett J.,McDonald, Robert,Ferguson, Michael J.,Stradiotto, Mark
experimental part, p. 1056 - 1071 (2012/02/15)
We report a diverse demonstration of synthetically useful chemoselectivity in the synthesis of di-, tri-, and tetraamines (62 examples) by use of Buchwald-Hartwig amination employing a single catalyst system ([Pd(cinnamyl)Cl]2/L1; L1 = N-(2-(di(1-adamantyl)phosphino)phenyl) morpholine, Mor-DalPhos). Competition reactions established the following relative preference of this catalyst system for amine coupling partners: linear primary alkylamines and imines > unhindered electron-rich primary anilines, primary hydrazones, N,N-dialkylhydrazines, and cyclic primary alkylamines > unhindered electron-deficient primary anilines, α-branched acyclic primary alkylamines, hindered electron-rich primary anilines ? cyclic and acyclic secondary dialkylamines, secondary alkyl/aryl and diarylamines, α,α-branched primary alkylamines, and primary amides. The new isomeric ligand N-(4-(di(1-adamantyl)phosphino)phenyl)morpholine (p-Mor-DalPhos, L2) was prepared in 63% yield and was crystallographically characterized; the [Pd(cinnamyl)Cl]2/L2 catalyst system exhibited divergent reactivity. Application of the reactivity trends established for [Pd(cinnamyl)Cl] 2/L1 toward the chemoselective synthesis of di-, tri-, and tetraamines was achieved. Preferential arylation was observed at the primary alkylamine position within 2-(4-aminophenyl)ethylamine with [Pd(cinnamyl)Cl] 2/L1 and 4-chlorotoluene (affording 5a); the alternative regioisomer (5a′) was obtained when using [Pd(cinnamyl)Cl]2/L2. These observations are in keeping with coordination chemistry studies, whereby binding of 2-(4-aminophenyl)ethylamine to the in situ generated [(L1)Pd(p-tolyl)] + fragment occurred via the primary amine moiety, affording the crystallographically characterized adduct [(L1)Pd(p-tolyl)(NH2CH 2CH2(4-C6H4NH2)] +OTf- (7) in 72% yield.
A highly versatile catalyst system for the cross-coupling of aryl chlorides and Amines
Lundgren, Rylan J.,Sappong-Kumankumah, Antonia,Stradiotto, Mark
supporting information; experimental part, p. 1983 - 1991 (2010/07/03)
The syntheses of 2-(di-tertbutylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamantylphosphino)-N,N-dimethylaniline (L2, 74%), and their application in BuchwaldHartwig 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 imines, 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), [PdCl 2(MeCN)2], or [Pd2(dba)3] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(allyl)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 ortto-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 cross-coupling of aryl chlorides and amines
Highly reactive, general and long-lived catalysts for palladium-catalyzed amination of heteroaryl and aryl chlorides, bromides, and iodides: Scope and structure-activity relationships
Shen, Qilong,Ogata, Tokutaro,Hartwig, John F.
, p. 6586 - 6596 (2008/12/22)
We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts containing sterically hindered chelating alkylphosphines for the amination of heteroaryl and aryl chlorides, bromides, and iodides. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides, and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides, and iodides occur to completion with 0.0005-0.05 mol % catalyst. A comparison of the reactivity of this catalyst for the coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Studies on structural variants of the most active catalyst indicate that a rigid backbone in the bidentate structure, strong electron donation, and severe hindrance all contribute to its high reactivity. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes.
Monolayer and Bilayer Vesicle Membranes from p-Phenylenediamine Derivatives
Fuhrhop, Juergen-Hinrich,Bartsch, Herbert
, p. 802 - 815 (2007/10/02)
Several water-insoluble (pH 4 or 2) N,N-dialkylated p-phenylenediamine derivatives from bilayer membrane vesicles on sonication under nitrogen.Corresponding α,ω-betaines give vesicles with monolayer membranes on sonication.In electron micrographs chain-li
