5542-49-4Relevant academic research and scientific papers
Palladium-Catalyzed C-H Amination/[2 + 3] or [2 + 4] Cyclization via C(sp3or sp2)-H Activation
An, Yang,Ding, Ya-Nan,Gou, Xue-Ya,Li, Qiao,Li, Yuke,Liang, Yong-Min,Zhang, Xiao-Yan,Zhang, Zhe
, p. 7961 - 7965 (2021/10/25)
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.
Catalytic N-Acylation of Cyclic Amines by Arylglyoxylic Acids via Radical-Radical Cross-Coupling
Bhadra, Sukalyan,Gupta, Aniket,Kumar Singh, Anupam,Rahaman, Ajijur
supporting information, p. 2198 - 2202 (2021/07/22)
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.
A carboxylate-assisted amination/unactivated C(sp2)-H arylation reactionviaa palladium/norbornene cooperative catalysis
An, Yang,Zhang, Bo-Sheng,Zhang, Zhe,Liu, Ce,Gou, Xue-Ya,Ding, Ya-Nan,Liang, Yong-Min
, p. 5933 - 5936 (2020/06/04)
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.
Palladium-Catalyzed Amination/Dearomatization Reaction of Indoles and Benzofurans
Zhang, Zhe,Zhang, Bo-Sheng,Li, Kai-Li,An, Yang,Liu, Ce,Gou, Xue-Ya,Liang, Yong-Min
, p. 7817 - 7839 (2020/07/16)
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.
DMAP and PivOH-promoted amination/allenization reaction
Zhang, Bo-Sheng,Li, Yuke,Gou, Xue-Ya,Zhang, Zhe,An, Yang,Wang, Xin-Gang,Liang, Yong-Min
supporting information, p. 9202 - 9205 (2020/08/26)
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
Palladium-Catalyzed Chemoselective Synthesis of 2-Aminocinnamyl Esters via Sequential Amination and Olefination of Aryl Iodides
Chen, Yanhui,Lv, Weiwei,Ba, Dan,Wen, Si,Cheng, Guolin
, p. 13280 - 13289 (2020/11/26)
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.
Direct N-O bond formation via oxidation of amines with benzoyl peroxide
Banerjee, Amit,Yamamoto, Hisashi
, p. 2124 - 2129 (2019/02/20)
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.
Copper- and Cobalt-Catalyzed Syntheses of Thiophene-Based Tertiary Amines
Bouarfa, Salima,Gra?l, Simon,Ivanova, Maria,Langlais, Timothy,Bentabed-Ababsa, Ghenia,Lassagne, Frédéric,Erb, William,Roisnel, Thierry,Dorcet, Vincent,Knochel, Paul,Mongin, Florence
, p. 3244 - 3258 (2019/06/08)
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.
Copper-Catalyzed Dihydroquinolinone Synthesis from Isocyanides and O-Benzoyl Hydroxylamines
Yang, Zhen,Jiang, Kun,Chen, Ying-Chun,Wei, Ye
, p. 3725 - 3734 (2019/03/20)
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
Copper-Catalyzed Three-Component Carboamination of Arynes: Expeditious Synthesis of o-Alkynyl Anilines and o-Benzoxazolyl Anilines
Niu, Sheng-Li,Hu, Jiangtao,He, Kuicheng,Chen, Ying-Chun,Xiao, Qing
supporting information, p. 4250 - 4254 (2019/06/07)
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.
