57318-64-6Relevant articles and documents
Nickel-catalysed couplings of aryl chlorides with secondary amines and piperazines
Brenner, Eric,Schneider, Raphael,Fort, Yves
, p. 12829 - 12842 (1999)
The reaction of aryl chlorides with secondary amines or piperazines in the presence of an in situ generated liganded nickel catalyst gives arylamines in good yields. Our process provides a mild, convenient and cheap method of arylamination starting from readily available substrates.
Effect of the 3- and 4-methyl groups on the opioid receptor properties of N-substituted trans -3,4-dimethyl-4-(3-hydroxyphenyl)piperidines
Kormos, Chad M.,Cueva, Juan Pablo,Gichinga, Moses G.,Runyon, Scott P.,Thomas, James B.,Brieaddy, Lawrence E.,Mascarella, S. Wayne,Gilmour, Brian P.,Navarro, Hernán A.,Carroll, F. Ivy
, p. 3140 - 3147 (2014/05/06)
N-substituted trans-3,4-dimethyl-4-(3-hydroxyphenyl)piperidines (2a,b) are opioid receptor antagonists where the antagonist properties are not due to the type of N-substituent. In order to gain a better understanding of the contribution that the 3- and 4-methyl groups make to the pure antagonist properties of 2a,b, we synthesized analogues of 2a,b that lacked the 4-methyl (5a,b), 3-methyl (6a,b), and both the 3- and 4-methyl group (7a,b) and compared their opioid receptor properties. We found that (1) all N-methyl and N-phenylpropyl substituted compounds were nonselective opioid antagonists (2) all N-phenylpropyl analogues were more potent than their N-methyl counterparts, and (3) compounds 2a,b which have both a 3- and 4-methyl substituent, were more potent antagonists than analogues 5a,b, 6a,b, and 7a,b. We also found that the removal of 3-methyl substituent of N-methyl and N-phenylpropyl 3-methyl-4-(3-hydroxyphenyl)piperazines (8a,b) gives (4a,b), which are opioid antagonists.
Transition metal-free amination of aryl halides-A simple and reliable method for the efficient and high-yielding synthesis of N-arylated amines
Bolliger, Jeanne L.,Frech, Christian M.
supporting information; experimental part, p. 1180 - 1187 (2009/04/10)
A simple and reliable reaction protocol for the clean, fast, and high-yielding synthesis of various N-arylated amines derived from reactions of aryl halides with various (also sterically hindered) amines under transition metal-free reaction conditions is presented. Dioxane and KN(Si(CH3)3)2 were found to be the ideal solvent and base for this transformation. The conversion rates and yields observed are excellent and in the majority of the reactions performed significantly higher than that obtained in their catalyzed versions. Furthermore, the selective synthesis of 6-halopyridin-2-amines and asymmetric pyridine-2,6-diamines (derived from consecutive reactions of 2,6-dibromopyridine and 2,6-dichloropyridine, respectively, with different amines) is possible in almost quantitative yields (relative to 2,6-dihalopyridine) within very short reaction times. Purification of the 6-halopyridin-2-amine intermediates is not necessary, allowing the synthesis of pyridine-2,6-diamines in 'one-pot'. However, catalysts are in many cases not required to efficiently and selectively couple aryl halides with amines, making transition metal-free versions of the Buchwald-Hartwig reaction extremely attractive for the synthesis of N-arylated amines with substrates containing substituents on the aryl halide, which either promote regioselectivity and/or do not require regioselective aminations.
Nickel(0)/dihydroimidazol-2-ylidene complex catalyzed coupling of aryl chlorides and amines
Desmarets, Christophe,Schneider, Raphael,Fort, Yves
, p. 3029 - 3036 (2007/10/03)
A general and simple nickel-catalyzed coupling of aryl chlorides and amines is reported. The scope and limitations of the coupling process using Ni(0), 1,3-bis(2,6-diisopropylphenyl)dihydroimidazol-2-ylidene, and NaO-t-Bu as base were investigated. Secondary cyclic and acyclic amines and anilines provided the arylamine coupling products in good to excellent yields. Compared to palladium-catalyzed aminations, this procedure offers an alternative route to N-substituted anilines starting from readily available aryl chlorides.
Direct Substitution of Aromatic Ethers by Lithium Amides. A New Aromatic Amination Reaction
Hoeve, Wolter ten,Kruse, Chris, G.,Luteyn, Jan M.,Thiecke, Janet R. G.,Wynberg, Hans
, p. 5101 - 5106 (2007/10/02)
Reaction of lithiated dialkylamines with methoxy aromatics in refluxing THF leads to products resulting from a direct ipso-substitution.Especially with lithiated secondary amines high conversions and selectivities are achieved.Sulfonyl-substituted aromatics react equally well, but halogenated aromatics give rise to side-products arising from a competing pathway via aryne intermediates.The scope and mechanistic implications of this novel nucleophilic amination reaction are described.
A NEW APPROACH TO THE SYNTHESIS OF ARYLDIFLUOROPHOSHINES. FORMATION OF CIS-DICHLORO-BIS(ARYLDIFLUOROPHOSPHINE)PLATINUM(II) COMPLEXES
Heuer, Lutz,Schmutzler, Reinhard
, p. 197 - 216 (2007/10/02)
Reaction of chlorodifluorophosphine with aryllithium compounds has been found to furnish aryldifluorophosphines.This type of reaction is applicable to any aromatic system for which a regioselective lithiation is possible.The most stable products are those
