- Palladium-Catalyzed C-H Amination/[2 + 3] or [2 + 4] Cyclization via C(sp3or sp2)-H Activation
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This report describes a palladium-catalyzed Catellani reaction consisting of amination/[2 + 3] or [2 + 4] cyclization via a carboxylate ligand-exchange strategy. This method effectively activates ortho-substituents that avoid a second C-H palladation. The scope of substrates was broad, o-methyl-substituted iodoarenes were applied to the reaction smoothly, and o-phenyl-substituted iodoarenes can also be obtained by this method. In terms of mechanism, density functional theory calculations proved the sequence of the key five-membered aryl-norbornene-palladacycle intermediate formation and C(sp3 or sp2)-H activation.
- An, Yang,Ding, Ya-Nan,Gou, Xue-Ya,Li, Qiao,Li, Yuke,Liang, Yong-Min,Zhang, Xiao-Yan,Zhang, Zhe
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p. 7961 - 7965
(2021/10/25)
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- Catalytic N-Acylation of Cyclic Amines by Arylglyoxylic Acids via Radical-Radical Cross-Coupling
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A methodical mechanistic investigation allowed for the catalytic N-acylation of secondary cyclic amine counterparts by arylglyoxylic acids through radical-radical coupling. The reaction proceeds via a twofold SET-promoted Cu(I)/Cu(II) catalytic cycle under mild conditions. An analogous reaction variant allows for the N-acylation in a one-pot fashion directly starting from a secondary cyclic amine even in the presence of a second amine or hydroxy group.
- Bhadra, Sukalyan,Gupta, Aniket,Kumar Singh, Anupam,Rahaman, Ajijur
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supporting information
p. 2198 - 2202
(2021/07/22)
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- A carboxylate-assisted amination/unactivated C(sp2)-H arylation reactionviaa palladium/norbornene cooperative catalysis
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This report describes a carboxylate-assisted palladium-catalysed Catellani reaction, which is compatible withortho-amination and unactivated C(sp2)-H arylation. This method was used to synthesize a series of 1-amino substituted dihydrophenanthridines, phenanthridines and 6H-benzo[c]chromenes. Based on kinetic isotope experiments, the kinetic curve proves that pivalic acid accelerates the reaction rate of unactivated C(sp2)-H activation, and thus this rate can keep up with the five membered aryl-norbornene-palladacycle (ANP) intermediate.
- An, Yang,Zhang, Bo-Sheng,Zhang, Zhe,Liu, Ce,Gou, Xue-Ya,Ding, Ya-Nan,Liang, Yong-Min
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p. 5933 - 5936
(2020/06/04)
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- Palladium-Catalyzed Amination/Dearomatization Reaction of Indoles and Benzofurans
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This report describes a palladium-catalyzed dearomatization and amination tandem reaction of 2,3-disubstituted indoles and benzofurans via the Catellani strategy. This reaction provides a new method for the construction of amino-substituted indoline-fused cyclic and benzofuran spiro compounds in good yields. The reaction has broad functional group compatibility and substrate scope.
- Zhang, Zhe,Zhang, Bo-Sheng,Li, Kai-Li,An, Yang,Liu, Ce,Gou, Xue-Ya,Liang, Yong-Min
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p. 7817 - 7839
(2020/07/16)
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- DMAP and PivOH-promoted amination/allenization reaction
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This report described the first DMAP and PivOH-promoted ortho-C-H amination and ipso-allenization reaction of iodobenzenes realized by Pd/norbornene cooperative catalysis. Based on control experiments and DFT calculations, we speculated that the three ligands have different functions and mechanism paths in the reaction. This journal is
- Zhang, Bo-Sheng,Li, Yuke,Gou, Xue-Ya,Zhang, Zhe,An, Yang,Wang, Xin-Gang,Liang, Yong-Min
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supporting information
p. 9202 - 9205
(2020/08/26)
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- Palladium-Catalyzed Chemoselective Synthesis of 2-Aminocinnamyl Esters via Sequential Amination and Olefination of Aryl Iodides
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We report a highly chemoselective palladium-catalyzed Catellani-type amination of aryl iodides terminated by the Heck reaction using allylic esters as terminating reagents. 2-Aminocinnamyl esters were formed exclusively via β-H elimination rather than β-OAc elimination without the assistance of a silver salt. This protocol represents a useful extension of Catellani-type transformations.
- Chen, Yanhui,Lv, Weiwei,Ba, Dan,Wen, Si,Cheng, Guolin
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p. 13280 - 13289
(2020/11/26)
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- Direct N-O bond formation via oxidation of amines with benzoyl peroxide
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Herein, we report a general and efficient method for direct N-O bond formation without undesirable C-N bond (amide) formation starting from commercially available amines and benzoyl peroxide. The oxidation of 1,2-diamines to furnish bis-(benzoyloxy)-1,2-diamines is reported for the first time. We found that a significant amount of water (BPO?:?water = 3?:?1) in combination with Cs2CO3 is necessary to achieve high selectivity and yield. The reaction conditions are applicable to a wide range of 1,2-diamine and 1,2-disubstituted-1,2-diamine substrates. Additionally this method is highly applicable to primary and secondary amines. Further, the present method can access chiral bis-hydroxamic acids and bis-hydroxyl amines in just two steps from 1,2-diamines. The reaction conditions are simple, mild and inert atmosphere free. The synthetic potential of this methodology is further demonstrated in the short synthesis of a chiral BHA ligand.
- Banerjee, Amit,Yamamoto, Hisashi
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p. 2124 - 2129
(2019/02/20)
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- Copper- and Cobalt-Catalyzed Syntheses of Thiophene-Based Tertiary Amines
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Thienylzinc halides and related compounds prepared by deprotonation followed by transmetalation were used in copper-catalyzed amination using N-benzoyloxy secondary amines. By extending the reaction to 1,5-naphthyridine, it was showed that the competitive dimer formation observed in the case of thiophenes was linked with the low stability of some thienylamines rather than homocoupling. Interestingly, thienylzinc halides and related compounds prepared by transmetalation of thienylmagnesium halides, either prepared from their bromo-precursors or generated by deprotometalation, were satisfactorily employed in cobalt-catalyzed aminations. Finally, aminothiophenes were involved in copper-catalyzed mono- and di-N-arylations, affording differently substituted di- and triphenylamines.
- Bouarfa, Salima,Gra?l, Simon,Ivanova, Maria,Langlais, Timothy,Bentabed-Ababsa, Ghenia,Lassagne, Frédéric,Erb, William,Roisnel, Thierry,Dorcet, Vincent,Knochel, Paul,Mongin, Florence
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p. 3244 - 3258
(2019/06/08)
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- Copper-Catalyzed Dihydroquinolinone Synthesis from Isocyanides and O-Benzoyl Hydroxylamines
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A copper-catalyzed protocol has been realized for the rapid assembly of dihydroquinolinones from readily accessible isocyanides and O-benzoyl hydroxylamines. The reactions (10 mol % of CuOAc, 10 mol % of dppe, 3 equiv of PhONa, 30 °C) deliver various stru
- Yang, Zhen,Jiang, Kun,Chen, Ying-Chun,Wei, Ye
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p. 3725 - 3734
(2019/03/20)
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- Copper-Catalyzed Three-Component Carboamination of Arynes: Expeditious Synthesis of o-Alkynyl Anilines and o-Benzoxazolyl Anilines
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A copper-catalyzed three-component reaction of in situ formed arynes, terminal alkynes, and O-benzoylhydroxylamines has been developed. By adjusting reaction conditions, the nucleophiles in this transformation can be extended from terminal alkynes to benzoxazoles. These procedures provide a modular and facile approach to o-alkynyl anilines and o-benzoxazolyl anilines from easily available substrates in only one step.
- Niu, Sheng-Li,Hu, Jiangtao,He, Kuicheng,Chen, Ying-Chun,Xiao, Qing
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supporting information
p. 4250 - 4254
(2019/06/07)
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- Copper-Catalyzed Electrophilic Ortho C(sp2)-H Amination of Aryl Amines: Dramatic Reactivity of Bicyclic System
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A practical copper-catalyzed, 2-picolinamide-directed ortho C-H amination of anilines with benzoyl-protected hydroxylamines has been disclosed that proceeds smoothly without any external stoichiometric oxidant or additives. Remarkably, besides anilines, b
- Begam, Hasina Mamataj,Choudhury, Rajarshee,Behera, Ashok,Jana, Ranjan
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supporting information
p. 4651 - 4656
(2019/06/17)
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- Synthesis of C4-Aminated Indoles via a Catellani and Retro-Diels-Alder Strategy
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Highly functionalized 4-aminoindoles were synthesized via the three-component cross-coupling of o-iodoaniline, N-benzoyloxyamines, and norbornadiene. The Catellani and retro-Diels-Alder strategy was used in this domino process. o-Iodoaniline, with electron-donating and sterically hindered protecting groups, made the reaction selective toward o-C-H amination. On the basis of density functional theory calculations, the intramolecular Buchwald coupling of this reaction underwent a dearomatization and a 1,3-palladium migration process. The reasons for the control of the chemical selectivity by the protecting groups are given. Moreover, synthetic applications toward 4-piperazinylindole and a GOT1 inhibitor were realized.
- Zhang, Bo-Sheng,Li, Yuke,Zhang, Zhe,An, Yang,Wen, Yu-Hua,Gou, Xue-Ya,Quan, Si-Qi,Wang, Xin-Gang,Liang, Yong-Min
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supporting information
p. 9731 - 9738
(2019/06/24)
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- Synthesis of C4-Aminated Indoles via a Catellani and Retro-Diels-Alder Strategy
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Highly functionalized 4-aminoindoles were synthesized via the three-component cross-coupling of o-iodoaniline, N-benzoyloxyamines, and norbornadiene. The Catellani and retro-Diels-Alder strategy was used in this domino process. o-Iodoaniline, with electron-donating and sterically hindered protecting groups, made the reaction selective toward o-C-H amination. On the basis of density functional theory calculations, the intramolecular Buchwald coupling of this reaction underwent a dearomatization and a 1,3-palladium migration process. The reasons for the control of the chemical selectivity by the protecting groups are given. Moreover, synthetic applications toward 4-piperazinylindole and a GOT1 inhibitor were realized.
- Zhang, Bo-Sheng,Li, Yuke,Zhang, Zhe,An, Yang,Wen, Yu-Hua,Gou, Xue-Ya,Quan, Si-Qi,Wang, Xin-Gang,Liang, Yong-Min
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supporting information
(2019/06/24)
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- Pd-Catalyzed Alkene Diamination Reactions of Nitrogen Electrophiles: Synthesis of Cyclic Guanidines and Ureas Bearing Dialkylaminomethyl Groups
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The Pd-catalyzed coupling of N-allylguanidines or N-allylureas with O-benzoylhydroxylamine derivatives affords cyclic guanidines or cyclic ureas bearing dialkylaminomethyl groups. The desired products are obtained in good yield, and substrates bearing substituents at the allylic position are transformed with moderate diastereoselectivity. The mechanism of these reactions appears to involve anti-aminopalladation of the alkene, followed by a rare sp3C-sp3N bond-forming reductive elimination from an alkylpalladium complex that contains β-hydrogen atoms.
- Peterson, Luke J.,Kirsch, Janelle K.,Wolfe, John P.
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supporting information
p. 3513 - 3517
(2018/06/26)
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- Rhodium(III)-catalyzed C–H amination of 2-arylquinazolin-4(3H)-one with N-alkyl-O-benzoyl-hydroxylamines
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N-benzoate alkylamines were used as the aminating agents, a efficient Rh-catalyzed ortho C–H amination of 2-arylquinazolin-4(3H)-one has been reported. The reactions exhibit high efficient and good functional group tolerance. Exclusive 2,6-bis-aminated pr
- Zhang, Yuanguang,Huang, Jiang,Deng, Zhihong,Mao, Xunchun,Peng, Yiyuan
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supporting information
p. 2330 - 2337
(2018/04/09)
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- Copper-Catalyzed Regio- and Enantioselective Aminoboration of Unactivated Terminal Alkenes
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A CuCl/(R,R)-PTBP-BDPP-catalyzed regioselective and enantioselective aminoboration of simple and unactivated terminal alkenes with bis(pinacolato)diboron (pinB-Bpin) and hydroxylamines has been developed. The amino group and boryl group were incorporated
- Kato, Kodai,Hirano, Koji,Miura, Masahiro
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supporting information
p. 5775 - 5778
(2018/03/27)
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- Modular ipso/ ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene Cooperative Catalysis
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Palladium/norbornene (Pd/NBE) cooperative catalysis has emerged as a useful tool for preparing poly substituted arenes; however, its substrate scope has been largely restricted to aryl iodides. While aryl bromides are considered as standard substrates for Pd-catalyzed cross coupling reactions, their use in Pd/NBE catalysis remains elusive. Here we describe the development of general approaches for aryl bromide-mediated Pd/NBE cooperative catalysis. Through careful tuning the phosphine ligands and quenching nucleophiles, ortho amination, acylation and alkylation of aryl bromides have been realized in good efficiency. Importantly, various heteroarene substrates also work well and a wide range of functional groups are tolerated. In addition, the utility of these methods has been demonstrated in sequential cross coupling/ortho functionalization reactions, consecutive Pd/NBE-catalyzed difunctionalization to construct penta-substituted aromatics and two-step meta functionalization reactions. Moreover, the origin of the ligand effect in ortho amination reactions has been explored through DFT studies. It is expected that this effort would significantly expand the reaction scope and enhance the synthetic potential for Pd/NBE catalysis in preparing complex aromatic compounds.
- Dong, Zhe,Lu, Gang,Wang, Jianchun,Liu, Peng,Dong, Guangbin
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supporting information
p. 8551 - 8562
(2018/06/25)
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- Synthesis of Arylamines via Aminium Radicals
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Arylamines constitute the core structure of many therapeutic agents, agrochemicals, and organic materials. The development of methods for the efficient and selective construction of these structural motifs from simple building blocks is desirable but stil
- Svejstrup, Thomas D.,Ruffoni, Alessandro,Juliá, Fabio,Aubert, Valentin M.,Leonori, Daniele
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supporting information
p. 14948 - 14952
(2017/11/20)
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- Rapid Assembly of Diversely Functionalized Spiroindenes by a Three-Component Palladium-Catalyzed C?H Amination/Phenol Dearomatization Domino Reaction
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A novel palladium-catalyzed three-component reaction of phenol-derived biaryls with N-benzoyloxyamines and norbornadiene (NBD) has been developed for the assembly of highly functionalized spiroindenes. This domino process was realized through NBD-assisted C?H amination and phenol dearomatization by forming one C?N bond and two C?C bonds in a single step. Preliminary studies indicated that asymmetric control of this transformation was feasible with chiral ligands. Moreover, the potential synthetic utility of this methodology was highlighted by a series of further transformations.
- Fan, Liangxin,Liu, Jingjing,Bai, Lu,Wang, Yaoyu,Luan, Xinjun
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supporting information
p. 14257 - 14261
(2017/10/31)
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- Copper-catalyzed oxyamination of electron-deficient alkenes with N-acyloxyamines
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A Cu(i)-catalyzed direct intermolecular oxyamination of electron deficient alkenes is disclosed. This process is characterized by difunctionalization of a variety of α,β-unsaturated ketones with easily available N-acyloxyamine reagents as both amine and oxygen donors, which delivers ester derivatives of β-amino alcohols in good yields as well as with high regioselectivity. Control studies suggested the involvement of alkyl radical species on the way of product formation.
- Ren, Shichao,Song, Shengjin,Ye, Lu,Feng, Chao,Loh, Teck-Peng
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supporting information
p. 10373 - 10376
(2016/09/02)
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- Synthesis of N,N,O-Trisubstituted Hydroxylamines by Stepwise Reduction and Substitution of O-Acyl N,N-Disubstituted Hydroxylamines
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Diverse N,N,O-trisubstituted hydroxylamines, an under-represented group in compound collections, are readily prepared by partial reduction of N-acyloxy secondary amines with diisobutylaluminum hydride followed by acetylation and reduction of the so-formed O-acyl-N,N-disubstituted hydroxylamines with triethylsilane and boron trifluoride etherate. Use of carbon nucleophiles in the last step, including allyltributylstannane, silyl enol ethers, and 2-methylfuran, gives N,N,O-trisubstituted hydroxylamines with branching α- to the O-substituent. N,N-Disubstiuted hydroxylamines are conveniently prepared by reaction of secondary amines with dibenzoyl peroxide followed by diisobutylaluminum hydride reduction.
- Dhanju, Sandeep,Crich, David
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supporting information
p. 1820 - 1823
(2016/05/19)
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- Palladium-Catalyzed Norbornene-Mediated Tandem Amination/Cyanation Reaction: A Method for the Synthesis of ortho-Aminated Benzonitriles
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A palladium-catalyzed, norbornene-mediated tandem amination/cyanation reaction via Catellani-type C-H functionalization was developed using N-benzoyloxyamines as the amination reagent and Zn(CN)2 as the terminating agent. This transformation, in which one C-N bond and one C-C bond are formed, provides an efficient approach for the synthesis of ortho-aminated benzonitriles in one pot from easily accessible starting materials.
- Luo, Bo,Gao, Jin-Ming,Lautens, Mark
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supporting information
p. 4166 - 4169
(2016/10/12)
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- Copper(I)-Catalyzed Interrupted Click Reaction: Synthesis of Diverse 5-Hetero-Functionalized Triazoles
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The 5-heterofunctionalized triazoles are important scaffolds in bioactive compounds, but current click reactions (CuAAC) cannot produce these core structures. A copper(I)-catalyzed interrupted click reaction to access diverse 5-functionalized triazoles is reported. Various 5-amino-, thio-, and selenotriazoles were readily assembled in one step in high yields. The reaction proceeds under mild conditions with complete regioselectivity. It also features a broad substrate scope and good functional group compatibility.
- Wang, Weiguo,Peng, Xianglong,Wei, Fang,Tung, Chen-Ho,Xu, Zhenghu
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supporting information
p. 649 - 653
(2016/02/27)
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- Palladium-Catalyzed Norbornene-Mediated Tandem ortho-C-H-Amination/ipso-C-I-Cyanation of Iodoarenes: Regiospecific Synthesis of 2-Aminobenzonitrile
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Efficient tandem ortho-C-H-amination/ipso-cyanation of iodoarenes was accomplished under a norbornene-mediated Pd-catalyzed process. A series of functionalized 2-aminobenzonitriles with much potential in the pharmaceutical industry were obtained by this p
- Majhi, Biju,Ranu, Brindaban C.
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supporting information
p. 4162 - 4165
(2016/11/05)
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- Copper(II)-catalyzed electrophilic amination of quinoline N-oxides with O-benzoyl hydroxylamines
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Copper acetate-catalyzed C-H bond functionalization amination of quinoline N-oxides was achieved using O-benzoyl hydroxylamine as an electrophilic amination reagent, thereby affording the desired products in moderate to excellent yields. Electrophilic amination can also be performed in good yield on a gram scale. This journal is
- Li, Gang,Jia, Chunqi,Sun, Kai,Lv, Yunhe,Zhao, Feng,Zhou, Kexiao,Wu, Hankui
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supporting information
p. 3207 - 3210
(2015/03/30)
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- PdII-Catalyzed Intermolecular Amination of Unactivated C(sp3)-H Bonds
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PdII-catalyzed intermolecular amination of unactivated C(sp3)-H bonds has been successfully developed for the first time. This method provides a new way to achieve the challenging intermolecular amination of unactivated C(sp3/s
- Gou, Quan,Liu, Gang,Liu, Zi-Ning,Qin, Jun
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supporting information
p. 15491 - 15495
(2015/11/03)
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- Broad scope hydrofunctionalization of styrene derivatives using iron-catalyzed hydromagnesiation
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The highly regioselective iron-catalyzed formal hydrofunctionalization of styrene derivatives with a diverse range of electrophiles has been developed using a single, operationally simple hydromagnesiation procedure and only commercially available, bench-stable reagents. Using just 0.5 mol % FeCl2·4H2O and N,N,N',N'-tetramethylethylenediamine, hydromagnesiation and electrophilic trapping have been used to form new carbon-carbon bonds (13 examples) and carbon-heteroatom bonds (5 examples) including the products of formal cross-coupling reactions, hydroboration, hydroamination, hydrosilylation, and hydrofluorination.
- Jones, Alison S.,Paliga, James F.,Greenhalgh, Mark D.,Quibell, Jacob M.,Steven, Alan,Thomas, Stephen P.
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supporting information
p. 5964 - 5967
(2015/01/08)
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- Copper-catalyzed enantioselective formal hydroamination of oxa- and azabicyclic alkenes with hydrosilanes and hydroxylamines
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A CuCl/(R,R)-Ph-BPE-catalyzed enantioselective formal hydroamination of oxa- and azabicyclic alkenes with polymethylhydrosiloxane (PMHS) and O-benzoylhydroxylamines has been developed. The efficient and stereoselective net addition of hydrogen and nitrogen atoms provides the corresponding optically active oxa- and azanorbornenyl- and -norbornanylamines in good yields and good enantiomeric ratios.
- Miki, Yuya,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information
p. 1498 - 1501
(2014/04/03)
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- Palladium/norbornene-mediated tandem C-H amination/C-I alkenylation reaction of aryl iodides with secondary cyclic O-benzoyl hydroxylamines and activated terminal olefins
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A novel palladium-catalyzed norbornene-mediated three-component reaction for the construction of ortho-alkenyl aromatic tertiary amines has been achieved, which represents a useful extension of the Catellani-type tandem ortho-selective C-H amination trans
- Chen, Zhi-Yuan,Ye, Chang-Qing,Zhu, Hui,Zeng, Xing-Ping,Yuan, Jian-Jun
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supporting information
p. 4237 - 4241
(2014/05/06)
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- Synthesis of 2-aminobenzoxazoles via copper-catalyzed electrophilic amination of benzoxazoles with O-benzoyl hydroxylamines
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An efficient copper-catalyzed electrophilic amination of benzoxazoles with O-benzoyl hydroxylamines is described, employing CuCl catalyst, PPh3 ligand, and LiOtBu base. This simple air-stable copper catalysis enables the preparation of various 2-aminobenzoxazole derivatives at room temperature in good yields.
- Yotphan, Sirilata,Beukeaw, Danupat,Reutrakul, Vichai
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supporting information
p. 6627 - 6633
(2013/07/26)
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- Ortho vs ipso: Site-selective pd and norbornene-catalyzed arene c-h amination using aryl halides
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A Pd and norbornene-catalyzed ortho-arene amination via Catellani-type C-H functionalization is reported. Aryl halides are used as substrates; N-benzoyloxyamines and isopropanol are employed as the amine source (oxidant) and reductant respectively. Exampl
- Dong, Zhe,Dong, Guangbin
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supporting information
p. 18350 - 18353
(2014/01/06)
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- Synthesis of hindered anilines: Copper-catalyzed electrophilic amination of aryl boronic esters
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No longer a hindrance: Copper-catalyzed electrophilic amination of aryl boronic esters is accomplished under mild reaction conditions using 2.5-5.0 mol % of a catalyst derived from copper tert-butoxide and Xantphos ligand (see scheme). The reaction tolerates a wide range of functional groups and can be used to prepare some of the most hindered anilines made to date. Copyright
- Rucker, Richard P.,Whittaker, Aaron M.,Dang, Hester,Lalic, Gojko
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supporting information; experimental part
p. 3953 - 3956
(2012/06/04)
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- An annulative electrophilic amination approach to 3-aminobenzoheteroles
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A copper-catalyzed annulative amination approach to 3-aminobenzofurans and -indoles from o-alkynylphenols and -anilines has been developed. The Cu-based catalysis is based on an umpolung, electrophilic amination with O-benzoyl hydroxylamines and enables t
- Matsuda, Naoki,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information; experimental part
p. 617 - 625
(2012/02/16)
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- Transition-metal-free electrophilic amination of arylboroxines
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A transition-metal-free strategy to construct C(sp2)-N bonds using arylboroxines and O-benzoyl hydroxylamines as coupling partners has been developed. This transformation provides a useful method to access various aromatic amines.
- Xiao, Qing,Tian, Leiming,Tan, Renchang,Xia, Ying,Qiu, Di,Zhang, Yan,Wang, Jianbo
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supporting information; experimental part
p. 4230 - 4233
(2012/09/22)
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- Copper-catalyzed annulative amination of ortho -alkynylphenols with hydroxylamines: Synthesis of 3-aminobenzofurans by umpolung amination strategy
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Chemical equations presented. A room temperature copper-catalyzed annulative amination of ortho-alkynylphenols with electrophilic amination reagents, O-acylated hydroxylamines, proceeds efficiently to provide the corresponding 3-aminobenzofurans of biolog
- Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information; body text
p. 2395 - 2397
(2011/06/28)
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- Copper-catalyzed electrophilic amination of organozinc nucleophiles: Documentation of O-benzoyl hydroxylamines as broadly useful R2N(+) and RHN(+) synthons
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This paper details new copper-catalyzed electrophilic amination reactions of diorganozinc reagents using O-benzoyl hydroxylamines as electrophilic nitrogen sources that may be accessed in one step. Simple and functionalized aryl, heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl nucleophiles couple with R2NOC(O)Ph and RHNOC(O)Ph reagents in the presence of catalytic quantities of copper salts to provide tertiary and secondary amines, respectively, in generally good yields. In many cases, the product may be isolated analytically pure after a simple extractive workup. The amination process is shown to tolerate a significant degree of steric demand. The amination of nominally unreactive Caryl-H bonds via a sequential directed ortho metalation/transmetalation/catalytic amination reaction sequence is detailed. The direct Cu-catalyzed amination of Grignard reagents using cocatalysis by ZnCl2 is described.
- Herman, Ashley M.,Johnson, Jeffrey S.
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p. 219 - 224
(2007/10/03)
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- Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents
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The copper-catalyzed electrophilic amination of diorganozinc reagents employing O-acyl N,N-dialkyl hydroxylamine derivatives as aminating agents is described. This reaction offers a general method for the preparation of tertiary amines in high yields and is noteworthy for its convenience both in terms of reaction conditions employed (room temperature, ≤1 h) and ease of product isolation (acid/base extractive workup). Copyright
- Berman, Ashley M.,Johnson, Jeffrey S.
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p. 5680 - 5681
(2007/10/03)
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