- Copper-catalyzed 1,2-amino oxygenation of 1,3-dienes: A chemo-, regio-, and site-selective three-component reaction with o-acylhydroxylamines and carboxylic acids
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A three-component reaction for 1,2-amino oxygenation of 1,3-dienes has been achieved using O-acyl hydroxylamines and carboxylic acids. The reaction occurs through copper-catalyzed amination of olefins followed by nucleophilic addition of carboxylic acids, offering high levels of chemo-, regio-, and site-selectivity. The method is effective for both terminal and internal 1,3-dienes, including those bearing multiple, unsymmetrical substituents. The amino oxygenation conditions also exhibited remarkable selectivity toward 1,3-dienes over alkenes, good tolerance of sensitive functional groups, and reliable scalability.
- Hemric, Brett N.,Chen, Andy W.,Wang, Qiu
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- Copper-Catalyzed Deoxygenative C-2 Amination of Quinoline N-Oxides
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An unprecedented reaction between quinoline N-oxides with O-benzoylhydroxylamines was developed by using CuCl as catalyst, generating deoxygenative products of 2-aminoquinolines in good yields. 1,2-Dichloroethane (DCE) as solvent was also served as reduci
- Wang, Zhihui,Han, Man-Yi,Li, Pinhua,Wang, Lei
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- (Diacetoxy)iodobenzene-Mediated Oxidative C-H Amination of Imidazopyridines at Ambient Temperature
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(Diacetoxy)iodobenzene (PIDA)-mediated direct oxidative C-H amination for the synthesis of 3-amino substituted imidazopyridines has been achieved under metal-free conditions at room temperature in short reaction times. This methodology is also applicable for the regioselective amination of indolizines. Experimental results suggest that the reaction likely proceeds through a radical pathway.
- Mondal, Susmita,Samanta, Sadhanendu,Jana, Sourav,Hajra, Alakananda
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- Copper-Catalyzed Diamination of Unactivated Alkenes with Electron-Rich Amino Sources
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The catalytic intermolecular diamination of unactivated alkenes with electron-rich amino sources is a challenge. Herein, by employing a directing-group strategy, a copper-catalyzed diamination of unactivated alkenes was realized. Symmetrical diamines were efficiently produced in a highly diastereoselective manner with readily available dialkylamines as amino sources, while a one-pot and two-step operation was necessary to produce the unsymmetrical diamines. These reactions were proposed to proceed through aziridinium intermediates.
- Li, Yang,Ali, Arshad,Dong, Junchao,Zhang, Yu,Shi, Lili,Liu, Qun,Fu, Junkai
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- Copper-Catalyzed Aminoheteroarylation of Unactivated Alkenes through Distal Heteroaryl Migration
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We report a copper-catalyzed aminoheteroarylation of unactivated alkenes to access valuable heteroarylethylamine motif. The developed reaction features a copper-catalyzed intermolecular electrophilic amination of the alkenes followed by a migratory heteroarylation. The method applies to alcohol-, amide-, and ether-containing alkenes, overcoming the common requirement of a hydroxyl motif in previous migratory difunctionalization reactions. This reaction is effective for the introduction of diverse aliphatic amines and has good functional group tolerance, which is particularly useful for rich functionalized heteroarenes. This migration-involved reaction was found well suited as a powerful ring-expansion approach for the construction of medium-sized rings that are in great demand in medicinal chemistry.
- Kwon, Yungeun,Zhang, Wei,Wang, Qiu
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p. 8807 - 8817
(2021/07/26)
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- Copper-Catalyzed Aminoarylation of Alkenes via Aminyl Radical Addition and Aryl Migration
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We describe a new strategy for aminoarylation of alkenes by copper-catalyzed smiles rearrangement using O-benzoylhydroxylamines as the amine reagent. This method affords various β-amino amide derivatives possessing a quaternary carbon center with wide functional group tolerance and high regioselectivity. The mechanistic studies indicate that the transformation can involve aminyl radical intermediates under acid-free condition.
- Liu, Mei-Ling,Liu, Xue-Yuan,Sun, Wen-Hui,Wang, Jin-Lin,Zou, Jian-Yu
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supporting information
(2022/01/04)
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- Haloamines as Bifunctional Reagents for Oxidative Aminohalogenation of Maleimides
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An unprecedented copper-catalyzed oxidative aminohalogenation of electron-deficient maleimides with secondary amines and NXS (X = Cl, Br, I) was developed, in which the N-X bonds generated in situ were used as difunctionalized reagents. The distinctive features of this multicomponent reaction include a simple green catalytic system, a spectral substrate range, and the late-stage modification of drug molecules. Most importantly, this umpolung radical cascade strategy exploits the in situ formation of N-iodoamines that enable efficient alkene aminoiodination.
- Zhou, Xueying,Yao, Yujing,Wang, Caihong,Xu, Yaling,Zhang, Wenliang,Ma, Yunfei,Wu, Ge
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supporting information
p. 3669 - 3673
(2021/05/10)
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- Directed Copper-Catalyzed Intermolecular Aminative Difunctionalization of Unactivated Alkenes
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A diverse collection of copper-catalyzed intermolecular aminative difunctionalizations of unactivated alkenes with N-halodialkylamines as the terminal dialkylamino source is reported. A bidentate auxiliary tethered on the alkene substrates is crucial, which can promote the migratory insertion of nonactivated alkenes into the aminyl radical-metal complex and stabilize the resultant high-valent copper intermediate to allow for further transformations. By employing this strategy, the intermolecular aminohalogenation reactions and a three-component aminoazidation reaction of unactivated alkenes with dialkylamino source were successively achieved in a remarkable regio- and stereoselective manner. These reactions were performed under neutral conditions and maintained excellent functional group tolerance toward a wide range of N-halodialkylamines and unactivated alkenes. Further mechanistic studies and DFT calculations supported a concerted migratory insertion of the C-C double bond into the aminyl radical-metal complex to form a Cu(III) intermediate.
- Li, Yang,Liang, Yujie,Dong, Junchao,Deng, Yi,Zhao, Chunyang,Su, Zhongmin,Guan, Wei,Bi, Xihe,Liu, Qun,Fu, Junkai
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supporting information
p. 18475 - 18485
(2019/11/19)
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- Catalyst- and Reagent-Free Electrochemical Azole C?H Amination
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Catalyst- and chemical oxidant-free electrochemical azole C?H aminations were accomplished via cross-dehydrogenative C?H/N?H functionalization. The catalyst-free electrochemical C?H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp3)?H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C?H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant.
- Qiu, Youai,Struwe, Julia,Meyer, Tjark H.,Oliveira, Jo?o C. A.,Ackermann, Lutz
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supporting information
p. 12784 - 12789
(2018/09/10)
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- Copper(II)-mediated intermolecular amination of inert C(sp3)[sbnd]H bonds with simple alkylamines to construct α,α-disubstituted β-amino acid derivatives
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Disclosed herein is a copper(II)-mediated chelation-assisted intermolecular amination of inert C(sp3)[sbnd]H bonds using simple alkylamines as the amino source. A straightforward and step-economic alternative to α,α-disubstituted β-amino acid derivatives is provided consequently. This reaction features good functional group tolerance and relatively broad substrate scope. Furthermore, a coupling product between morpholine and radical inhibitor 2,6-di-tert-butyl-p-cresol (BHT) was isolated, indicating that a single electron transfer (SET) process might be involved in this transformation.
- Wang, Chunxia,Yang, Yudong
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supporting information
p. 935 - 940
(2017/02/18)
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- Cobalt-Catalyzed Direct Amination of Arenes with Alkylamines via Bidentate-Chelation Assistance
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Cobalt-catalyzed C?H amination of arenes with alkylamines by the assistance of 8-aminoquinoline as auxiliary through sp2C?H bond functionalization has been achieved. Attractive features of this protocol include the low loading of the cobalt catalyst and the readily available reagents. (Figure presented.).
- Yan, Qiangqiang,Xiao, Tangxin,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 2707 - 2711
(2016/08/30)
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- Nickel-Catalyzed Direct Amination of Arenes with Alkylamines
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(Figure Presented) The efficient nickel-catalyzed direct amination of arenes with simple alkylamines has been achieved with the assistance of a bidentate directing group through sp2 C-H bond functionalization. Preliminary mechanistic investigations indicate that the reaction probably proceeds through a NiI/NiIII catalytic pathway.
- Yan, Qiangqiang,Chen, Zhengkai,Yu, Wenlong,Yin, Hong,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 2482 - 2485
(2015/05/27)
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- Reaction of 3,5-Di-tert-butyl-4-hydroxybenzyl Acetate with Amines
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3,5-Di-tert-butyl-4-hydroxybenzyl acetate reacts with primary and secondary amines to give mainly the corresponding benzylamines. Base-catalyzed transformation of 3,5-di-tert-butyl-4-hydroxybenzyl acetate into 2,6-di-tert-butyl-4-methylene-2,5-cyclohexadienone occurs to a small extent. The major product of the reaction of 3,5-di-tert-butyl-4-hydroxybenzyl acetate with aqueous ammonia is bis(3,5-di-tert-butyl-4-hydroxybenzyl) ether which is formed by the action of ammonium acetate liberated during the process.
- Bukharov,Nugumanova,Mukmeneva
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p. 1605 - 1608
(2007/10/03)
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- Method for treating multiple sclerosis
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Provided is a method of treating multiple sclerosis employing certain phenol and benzamide compounds.
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- Method of treating inflammatory bowel disease
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Provided is a method for treating inflammatory bowel disease in mammals utilizing certain phenol and benzamide compounds.
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- Method of treating type I diabetes
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Provided is a method for treating Type I diabetes in mammals utilizing certain phenol and benzamide compounds.
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- Method for treating inflammation
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Provided are methods of treating inflammation, arthritis and muscular dystrophy and preventing ischemia-induced cell damage employing certain phenol and benzamide compounds.
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- Chemical process
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Novel bis(3',5'-mono or dihydrocarbyl-4'-hydroxybenzyl)-1,3-diketones are prepared by reacting a (3',5'-mono or dihydrocarbyl-4'-hydroxybenzyl)-1,3-diketone with an N,N-dihydrocarbyl-2,6-mono or dihydrocarbyl-4-aminomethylphenol and an alkyl halide in the presence of an alkaline earth metal halide. The products are useful as antioxidants.
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