180336-49-6Relevant articles and documents
Helicity of N,N′-diaryl-trans-1,2-diaminocyclohexane derivatives. Implications for molecular helicity manipulations
Kwit,Gawronski
, p. 9323 - 9331 (2003)
Derivatives of trans-1,2-diaminocyclohexane (DACH), useful as chiral ligands, scaffolds and building blocks, differ in their conformation. The conformation of N,N′-diaryl-DACH derivatives was studied by the semiempirical and DFT computational methods and by exciton-coupled circular dichroism. It was found that, contrary to M-helical N,N′-diimine, N,N′-diimide and N,N′-diamide derivatives, the aromatic residues in N,N′-diphenyl derivatives are oriented to form a P-helix for the (R,R)-DACH absolute configuration. The helicity of the bis-aryl system is modified in the case of 1-naphthyl or 2-naphthyl derivatives. Further switching of helicity has been demonstrated by either protonation or mono-N-acetylation of N,N′-diaryl DACH derivatives.
Practical heterogeneous photoredox/nickel dual catalysis for C-N and C-O coupling reactions
Liu, Yi-Yin,Liang, Dong,Lu, Liang-Qiu,Xiao, Wen-Jing
supporting information, p. 4853 - 4856 (2019/05/02)
Efficient C-N and C-O coupling reactions of aryl halides with amines and alcohols have been developed by using the strategy of heterogeneous visible light photoredox and nickel dual catalysis. Obviously, the joint use of inexpensive and bench-stable CdS and nickel salts, together with mild reaction conditions, makes these two transformations attractive for the synthetic community. This heterogeneous dual catalysis system also proved to be successful in the ligand-free catalytic hydroxylation of aryl bromide with water as a nucleophile. The practicality of this protocol is further emphasized by the scaled-up reaction and the reusability of heterogeneous photocatalysts.
Two Component Recyclable Heterogeneous Catalyst, Process for Preparation Thereof and its Use for Preparation of Amines
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Page/Page column 6, (2012/01/13)
The invention describes the development of highly efficient, recyclable two component system, CuAl-hydrotalcite/rac 1,1′-Binaphthalene-2,2′-diol catalytic system for the N-alkylation of electron deficient aryl chlorides in presence of potassium carbonate as a base at room temperature in 3-6 h, wherein the process is provided for the preparation of various secondary amines via C—N coupling reaction of aliphatic amines(aliphatic open chain, acyclic, benzyl amines and heterocyclic amines) with various aryl chlorides.
OXIDATIVE HOMO-COUPLING REACTIONS OF ARYL BORONIC ACIDS USING A POROUS COPPER METAL-ORGANIC FRAMEWORK AS A HIGHLY EFFICIENT HETEROGENEOUS CATALYST
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Page/Page column 23-28, (2011/02/24)
The disclosure provides methods for the use of open metal frameworks to synthesize biaryls comprising contacting a metal organic framework (MOF) or metal organic polyhedral (MOP) with an aryl boronic acid compound under conditions wherein the MOF or MOP catalyze the synthesis of the biaryl through a homo-coupling reaction.
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.
[(CyPF-Bu)PdCI2]: An air-stable, one-component, highly efficient catalyst for amination of heteroaryl and aryl halides
Shen, Qilong,Hartwig, John F.
supporting information; experimental part, p. 4109 - 4112 (2009/05/27)
(Chemical Equation Presented) An air- and moisture-stable palladium catalyst, [(CyPF-1Bu)PdCI2] (1), for coupling of heteroaryl chlorides, bromides, and iodides with a variety of primary amines is described. Most of these reactions occurred in high yield with 0.001-0.05 mol % catalyst loading. The reactions tolerated a wide range of functional groups.
Scope and limitations of Pd2(dba)3/P(i-BuNCH 2CH2)3N-catalyzed Buchwald-Hartwig amination reactions of aryl chlorides
Urgaonkar, Sameer,Verkade, John G.
, p. 9135 - 9142 (2007/10/03)
Proazaphosphatrane ligands in combination with Pd2(dba) 3 generate highly active catalysts for Buchwald-Hartwig amination of aryl chlorides. In particular, commercially available P(i-BuNCH 2-CH2)3N is a highly general and efficient ligand, allowing the coupling of an electronically diverse set of aryl chlorides, including chloropyridines, with a wide variety of amines using 1 mol % of Pd at 100 °C. Either a 1:1 or 2:1 ratio of ligand to Pd was found to be effective. This catalyst system performs exceptionally well for sterically hindered substrates, even with only 0.25 mol % of Pd. It is shown that NaOH can also be used as the base (instead of NaO-t-Bu) allowing functionalized substrates to participate in these reactions.
One-pot reductive amination of aldehydes and ketones with α-picoline-borane in methanol, in water, and in neat conditions
Sato, Shinya,Sakamoto, Takeshi,Miyazawa, Etsuko,Kikugawa, Yasuo
, p. 7899 - 7906 (2007/10/03)
A one-pot reductive amination of aldehydes and ketones with amines using α-picoline-borane as a reducing agent is described. The reaction has been carried out in MeOH, in H2O, and in neat conditions in the presence of small amounts of AcOH. This is a highly efficient and mild procedure that is applicable for a wide variety of substrates. In particular, this is the first successful demonstration that this type of reaction can be carried out in water and in neat conditions.
P[N(i-Bu)CH2CH2]3N: A versatile ligand for the Pd-catalyzed amination of aryl chlorides
Urgaonkar, Sameer,Nagarajan,Verkade, John G.
, p. 815 - 818 (2007/10/03)
(Matrix presented) Palladium-catalyzed amination reactions of aryl chlorides with amines proceeded in the presence of the bicyclic triaminophosphine P[N(i-Bu)CH2CH2]3N to afford the corresponding arylamines in good to excellent yields. Electron-poor, electron-neutral, and electron-rich aryl chlorides all participated with equal ease.
