- Synthesis of N-heterocyclic carbene-Pd(II)-5-phenyloxazole complexes and initial studies of their catalytic activity toward the Buchwald-Hartwig amination of aryl chlorides
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Three new N-heterocyclic carbene (NHC)-Pd(II) complexes using 5-phenyloxazole as the ancillary ligand have been obtained in moderate to good yields by a one-pot reaction of the corresponding imidazolium salts, palladium chloride and 5-phenyloxazole under mild conditions. Initial studies showed that one of the complexes is an efficient catalyst for the Buchwald-Hartwig amination of aryl chlorides with various secondary and primary amines under the varied catalyst loading of 0.01-0.05 mol%, thus it will enrich the chemistry of NHCs and give an alternative catalyst for the coupling of challenging while cost-low aryl chlorides.
- Zhang, Zhi-Mao,Xu, Yu-Ting,Shao, Li-Xiong
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- Dehydrogenation/(3+2) Cycloaddition of Saturated Aza-Heterocycles via Merging Organic Photoredox and Lewis Acid Catalysis
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Herein, we report a photoinduced dehydrogenation/(3+2) cycloaddition reaction by merging organic photoredox and Lewis acid catalysis, providing a straightforward and efficient approach for directly installing a benzofuran skeleton on the saturated aza-heterocycles. In this protocol, we also describe a novel organic photocatalyst (t-Bu-DCQ) with the advantages of a wider redox potential, easy synthesis, and a low price. Furthermore, the stepwise activation mechanism of dual C(sp3)-H bonds was demonstrated by a series of experimental and computational studies.
- Xiao, Teng-Fei,Zhang, Yi-Fan,Hou, Wen-Tao,Yan, Pen-Ji,Hai, Jun,Xu, Peng-Fei,Xu, Guo-Qiang
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supporting information
p. 8942 - 8946
(2021/11/24)
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- Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application
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Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.
- Sinai, ádám,Simkó, Dániel Cs.,Szabó, Fruzsina,Paczal, Attila,Gáti, Tamás,Bényei, Attila,Novák, Zoltán,Kotschy, András
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supporting information
p. 1122 - 1128
(2020/03/03)
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- Tropane alkaloid compounds and method of manufacturing using sequential oxidation reactions
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The present invention relates to a tropane alkaloid compound sequentially using an oxidative Mannich ring reaction and a method for producing the same. The present invention provides a tropane alkaloid compound having a structure of chemical formula 1 in
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Paragraph 0098; 0129-0133
(2020/06/16)
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- Catalytic and Aerobic Oxidative Biaryl Coupling of Anilines Using a Recyclable Heterogeneous Catalyst for Synthesis of Benzidines and Bicarbazoles
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In this study, a heterogeneous rhodium-catalyzed oxidative homocoupling reaction of anilines utilizing molecular oxygen as the sole oxidant is reported. Employing a commercially available and recyclable Rh/C catalyst enabled the oxidative dimerization of various anilines, including N,N-disubstituted and N-monosubstituted anilines, as well as diarylamines, triarylamines, and carbazoles. Additionally, the catalytic protocol was extended to the ortho-ortho coupling of anilines, affording 2,2′-diaminobiphenyls with high regioselectivity. Notably, the developed approach provides rapid access to diversely functionalized benzidines and diaminobiphenyls in an operationally simple, practical, and environmentally friendly manner.
- Matsumoto, Kenji,Toubaru, Yasunori,Tachikawa, Shohei,Miki, Ayaka,Sakai, Kentaro,Koroki, Syota,Hirokane, Tsukasa,Shindo, Mitsuru,Yoshida, Masahiro
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p. 15154 - 15166
(2020/12/23)
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- Visible Light-Mediated (Hetero)aryl Amination Using Ni(II) Salts and Photoredox Catalysis in Flow: A Synthesis of Tetracaine
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We report a visible light-mediated flow process for C-N cross-coupling of (hetero)aryl halides with a variety of amine coupling partners through the use of a photoredox/nickel dual catalyst system. Compared to the method in batch, this flow process enables a broader substrate scope, including less-activated (hetero)aryl bromides and electron-deficient (hetero)aryl chlorides, and significantly reduced reaction times (10 to 100 min). Furthermore, scale up of the reaction, demonstrated through the synthesis of tetracaine, is easily achieved, delivering the C-N cross-coupled products in consistently high yield of 84% on up to a 10 mmol scale.
- Park, Boyoung Y.,Pirnot, Michael T.,Buchwald, Stephen L.
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p. 3234 - 3244
(2020/02/04)
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- N-Heterocyclic carbene-palladacyclic complexes: synthesis, characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides
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N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01 mol%).
- Liu, Feng,Hu, Yuan-Yuan,Li, Di,Zhou, Quan,Lu, Jian-Mei
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p. 5683 - 5690
(2018/08/24)
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- Dual C(sp3)?H Bond Functionalization of N-Heterocycles through Sequential Visible-Light Photocatalyzed Dehydrogenation/[2+2] Cycloaddition Reactions
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Herein we describe a mild method for the dual C(sp3)?H bond functionalization of saturated nitrogen-containing heterocycles through a sequential visible-light photocatalyzed dehydrogenation/[2+2] cycloaddition procedure. As a complementary approach to the well-established use of iminium ion and α-amino radical intermediates, the elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under mild conditions and efficiently captured by acetylene esters to form a wide array of bicyclic amino acid derivatives, thus enabling the simultaneous functionalization of two vicinal C(sp3)?H bonds.
- Xu, Guo-Qiang,Xu, Ji-Tao,Feng, Zhi-Tao,Liang, Hui,Wang, Zhu-Yin,Qin, Yong,Xu, Peng-Fei
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supporting information
p. 5110 - 5114
(2018/03/27)
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- Transition-Metal-Free Selective C?H Benzylation of Tertiary Arylamines by a Dearomatization-Aromatization Sequence
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Due to the significance of hybrid systems in drug discovery, there is an urgent need to assemble multiple biologically active ingredients into a single molecule. Here, we report a general transition-metal-free selective C?H benzylation of tertiary arylamines in good to excellent yields with a broad substrate scope and high functional-group tolerance under mild conditions. Besides arylamines, some other benzene derivatives also readily furnished the corresponding diaryl methane derivatives with this protocol. A series of control experiments and theoretical calculations indicated that this transition-metal-free reaction is a dearomatization-aromatization process.
- Xu, Guo-Qiang,Feng, Zhi-Tao,Xu, Ji-Tao,Wang, Zhu-Yin,Qin, Yong,Xu, Peng-Fei
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supporting information
p. 13778 - 13782
(2018/09/14)
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- N-heterocyclic carbene-palladium complex, and preparation method and application thereof
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The invention discloses an N-heterocyclic carbene-palladium complex, and a preparation method and application thereof. The N-heterocyclic carbene-palladium complex disclosed by the invention is shown in Formula (I), wherein L1 is a quinoline ligand or isoquinoline ligand, and N in the L1 is connected with Pd; L2 is an N-heterocyclic carbene ligand, and carbene carbon in the L2 is connected with the Pd; and X1 and X2 are respectively independently an anionic ligand. The N-heterocyclic carbene-palladium complex disclosed by the invention can efficiently catalyze carbon-carbon or carbon-heteroatom coupling reaction using aryl halide as a substrate. The formula is shown in the specification.
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Paragraph 0138; 0139
(2017/07/22)
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- Metal-free protocol for the synthesis of N-arylpyrrolidines catalyzed by hydrogen iodine
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A metal-free and efficient approach to N-arylpyrrolidines from arylamines and cyclic ethers catalyzed by hydrogen iodine is described. In this protocol, no additive is added and a wide range of N-arylpyrrolidines are synthesized with up to 99% yield. Reaction mechanism involving iodine radical is proposed.
- Hou, Tingting,Zhang, Chaofeng,Wang, Yehong,Liu, Zhenting,Zhang, Zhixin,Wang, Feng
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- Synthesis of N-heterocyclic carbene-PdCl2-(iso)quinoline complexes and their application in arylamination at low catalyst loadings
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A new type of N-heterocyclic carbene-PdCl2-(iso)quinoline complexes 3 were successfully achieved in acceptable to good yields from easily available starting materials under mild conditions, and their structures were unambiguously confirmed using X-ray single crystal diffraction. Furthermore, their catalytic activity toward Buchwald-Hartwig arylamination of aryl chlorides with primary and secondary amines was fully tested. Under the optimal reaction conditions, the expected arylated amines can be obtained in high to excellent yields at low catalyst loadings (0.005-0.05 mol%). It may be worth noting here that comparison of these complexes with other well-defined and easily available NHC-Pd(ii) complexes bearing different N-containing ancillary ligands was also carried out, showing their superior catalytic activity over all others.
- Liu, Feng,Zhu, Yi-Ran,Song, Lu-Gan,Lu, Jian-Mei
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p. 2563 - 2571
(2016/03/01)
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- Direct Acylation of C(sp3)-H Bonds Enabled by Nickel and Photoredox Catalysis
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Using nickel and photoredox catalysis, the direct functionalization of C(sp3)-H bonds of N-aryl amines by acyl electrophiles is described. The method affords a diverse range of α-amino ketones at room temperature and is amenable to late-stage coupling of complex and biologically relevant groups. C(sp3)-H activation occurs by photoredox-mediated oxidation to generate α-amino radicals which are intercepted by nickel in catalytic C(sp3)-C coupling. The merger of these two modes of catalysis leverages nickel's unique properties in alkyl cross-coupling while avoiding limitations commonly associated with transition-metal-mediated C(sp3)-H activation, including requirements for chelating directing groups and high reaction temperatures. Teamwork: The direct functionalization of C(sp3)-H bonds of N-aryl amines by acyl electrophiles is achieved, thus affording a diverse range of α-amino ketones at room temperature. C(sp3)-H activation occurs by photoredox-mediated oxidation to generate α-amino radicals which are intercepted by nickel in catalytic C(sp3)-C coupling.
- Joe, Candice L.,Doyle, Abigail G.
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supporting information
p. 4040 - 4043
(2016/03/19)
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- Catalytic Asymmetric Arylation of α-Aryl-α-diazoacetates with Aniline Derivatives
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The asymmetric arylation of diazo compounds with aniline derivatives cooperatively catalyzed by an achiral dirhodium complex and a chiral spiro phosphoric acid is reported. The reaction provides a new method for the facile synthesis of α-diarylacetates, v
- Xu, Bin,Li, Mao-Lin,Zuo, Xiao-Dong,Zhu, Shou-Fei,Zhou, Qi-Lin
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supporting information
p. 8700 - 8703
(2015/07/27)
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- Cycloaddition of Enamine and Iminium Ion Intermediates Formed in the Reaction of N -Arylpyrrolidines with T-HYDRO
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The reaction of N-arylpyrrolidine derivatives with 70% aqueous tert-butyl hydroperoxide (T-HYDRO) in the presence of NaOAc·3H2O gives tetracyclic amines in 59-78% yields via cycloaddition of the corresponding iminium ion and enamine intermediates formed in situ in cyclohexane solvent. The iminium ion intermediate reacts with t-BuOK in methanol to give the corresponding cyclic amides in 85-88% yields or undergoes alkylation to give the corresponding nitromethyl product in 74-79% yields using t-BuOK and nitromethane in methanol.
- Rao, Gunda Ananda,Periasamy, Mariappan
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p. 2231 - 2236
(2015/09/28)
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- Modular synthesis of functionalisable alkoxy-tethered N-heterocyclic carbene ligands and an active catalyst for buchwald-hartwig aminations
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Modular syntheses of functionalised, alkoxy-tethered 1,3-bis(2,4,6- trimethylphenyl)imidazolium (IMes*H+) and 1,3-bis(2,6- diisopropylphen-l)imidazolium (IPr*H+) derivatives 1,3-bis(4-alkyl- -2,4,6-trimethylphenyl)imidazolium (IXyOR*H+) and 1,3-bis(4-alkyl-oxy-2,6-diisopropylphenyl)imidazolium (IPrOR*H +) are reported. A reliable synthesis of the key starting material 4-amino-3,5-diisopropylphenol is also described. Etherification of hydroxydecorated ligand intermediates before formation of the imidazolium core and subsequent modification, or direct etherification of the versatile synthon IPrOH·HCl, allowed access to various linker types including triethoxysilyl, primary amino and norbornenyl, which are not accessible by other methods. An IPrOR-palladium(II) complex was prepared, and its catalytic activity was evaluated in challenging Buchwald- Hartwig aminations of aryl chlorides. This precatalyst displayed excellent activity and selectivity under mild reaction conditions, achieving in some cases a 10-fold improvement in TOF relative to the IPr-based version. An unexpected activity profile was observed wherein sterically demanding anilines were coupled more easily than those lacking orthosubstitution.
- Krinsky, Jamin L.,Martinez, Alberto,Godard, Cyril,Castillon, Sergio,Claver, Carmen
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supporting information
p. 460 - 474
(2014/05/20)
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- Synthesis of N-aryl substituted, five- and six-membered azacycles using aluminum-amide complexes
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Synthesis of N-aryl substituted, five- and six-membered azacycloalkanes, isoindolines and tetrahydroisoquinolines, has been described. In this synthesis, cyclic ethers (n = 1, 2) were treated with dimethylaluminum-amide reagents, derived from a range of aryl amines and trimethylaluminum, to afford the corresponding azacycles in good yields. This journal is the Partner Organisations 2014.
- Korbad, Balaji L.,Lee, Sang-Hyeup
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supporting information
p. 8985 - 8988
(2014/08/05)
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- Synthesis of N-arylsubstituted pyrrolidines and piperidines by reaction of anilines with α,ω-diols catalyzed by FeCl3·6H2O in carbon tetrachloride
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N-Arylpyrrolidines and N-arylpiperidines were synthesized in 20-88% yields by the reaction of aniline and aniline derivatives with 1,4-butane- and 1,5-pentanediols in the presence of Fecontaining catalysts and carbon tetrachloride. 1,4-Butane- and 1,5-pentanediols are partially chlorinated under the reaction conditions to give chlorohydrins, which subsequently undergo Nheterocyclization with anilines to give N-arylpyrrolidines and N-arylpiperidines.
- Khusnutdinov, Ravil I.,Bayguzina, Alfiya R.,Asylbaeva, Rigina S.,Aminov, Rishat I.,Dzhemilev, Usein M.
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p. 341 - 350
(2014/12/12)
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- N-heterocyclization of primary amines with dihalides using microreactors
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(Chemical Equation Presented) A practical, rapid, and efficient reaction using microreactors for the direct N-alkylation from aniline derivatives and alkyl dihalides has been achieved in the presence of aqueous potassium carbonate at an elevated temperature. This improved synthetic methodology provides a straightforward microfluid approach to the synthesis of a variety of N-aryl azacycloalkanes. Copyright Taylor & Francis Group, LLC.
- He, Hongjie,Lin, Qi,Liu, Xiaofeng,Yang, Yongtai,Zhou, Yaming,Jia, Yu,Gao, Xiang
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experimental part
p. 2512 - 2525
(2012/07/14)
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- MODULATORS OF CCR9 RECEPTOR AND METHODS OF USE THEREOF
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Provided are compounds that are modulators of CCR9 receptor activity, compositions containing the compounds and methods of use of the compounds and compositions. In certain embodiments, provided are methods for treating or ameliorating diseases associated
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Page/Page column 44-45
(2010/03/02)
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- An efficient silane-promoted nickel-catalyzed amination of aryl and heteroaryl chlorides
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(Chemical Equation Presented) A new silane-promoted nickel-catalyzed amination of aryl chlorides with 0.5 mol % of Ni(acac)2, 1 mol % of 3,5,6,8-tetrabromo-1,10-phenanthroline, and polymethylhydrosiloxane was developed. A broad range of aryl and heteroaryl chlorides can be coupled with secondary amines and anilines to give the desired (het)arylamines in good to excellent yields. The reaction is sensitive to the nature and amount of the silane promoter.
- Manolikakes, Georg,Gavryushin, Andrei,Knochel, Paul
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p. 1429 - 1434
(2008/04/05)
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- Anodic cyanation of 1-arylpyrrolidines
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The electrochemical cyanation of 1-arylpyrrolidines was carried out in methanol containing sodium cyanide at a platinum anode in a divided cell. The reaction gave the corresponding α-aminonitriles 2, together with the unexpected 1-arylpyrrolidine-2-carboximidic acid methyl esters 3 as byproducts.
- Liu, Wei,Ma, Yuan,Yin, Yingwu,Zhao, Yufen
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p. 577 - 579
(2007/10/03)
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- Aromatization of enamines promoted by a stoichiometric amount of palladium(II) salts: A novel method for the synthesis of aromatic amines
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Enamines (1a-r) prepared from cyclohexanones, cyclohexane-1,3-diones, or tetralones led to arylamines (2a-r) in one pot when treated with a stoichiometric amount of palladium salts [PdCl2-(MeCN)2] in acetonitrile in the presence of triethylamine at room temperature or at elevated temperature, in some cases for 5 min to 2 h. The initial electrophilic attack of palladium chloride on the β-carbon of the enamines led to a σ-palladium species (8) which triggered a series of reactions (→ 9 → 19 → 11 → 12) destined for aromatization to give 2a-r in good yields. The intervention of such a σ-palladium species has been attested by a trapping experiment. On the basis of this reaction mechanism, we have developed another new process capable of transforming acyclic compounds having 6-en-2-one frameworks (16, 23, 25) to arylamines (2s-u) when their enamines were treated under the similar conditions as above, featuring again the formation of σ-palladium species such as 8 as the initial key intermediate.
- Ishikawa,Uedo,Tani,Saito
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p. 186 - 191
(2007/10/03)
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- Nickel-catalysed couplings of aryl chlorides with secondary amines and piperazines
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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.
- Brenner, Eric,Schneider, Raphael,Fort, Yves
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p. 12829 - 12842
(2007/10/03)
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- Reductive one batch synthesis of N-substituted pyrrolidines from primary amines and 2,5-dimethoxytetrahydrofuran
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The construction of the pyrrolidine ring about a nitrogen of a primary amine by a reductive condensation reaction using 2,5- dimethoxytetrahydrofuran and sodium borohydride in acidic water medium is described. The reaction is fast, affords good to excellent yields and appears insensitive to electron effects and severe steric hindrance; it is found to be compatible with a large variety of aryl substituents, including nitro and oxo groups. The reaction allows the introduction of two deuterium atoms, with label conservation, in both the α-positions of the pyrrolidine ring by the use of sodium borodeuteride instead of sodium borohydride.
- Verardo, Giancarlo,Dolce, Anna,Toniutti, Nicoletta
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- New efficient nickel(0) catalysed amination of aryl chlorides
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It is shown that a liganded Ni(0) complex reagent, prepared in THF from NaH, t.AmOH, Ni(OAc)2 and 2,2'-bipyridine, efficiently catalyses amination of aryl chlorides under mild conditions.
- Brenner, Eric,Fort, Yves
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p. 5359 - 5362
(2007/10/03)
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- Synthesis of Pyrrolidines and Pyrrolidinones by the Rhodium Complex Catalyzed Cyclization of Unsaturated Amines
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N-Allylic arylamines react with carbon monoxide, sodium borohydride, 2-propanol, and catalytic amounts of the zwitterionic complex η6-C6H6BPh3-Rh(COD)+ (1), to form pyrrolidines as the main products in most cases.Pyrrolidinones result from N-allylic alkylamines.An alternate route to the lactams from N-allylic alkylamines involves synthesis gas instead of CO/NaBH4, together with the dual catalytic system 1/2.Complementary to the N-allylic arylamine route to pyrrolidines with NaBH4 and 1 is the use of synthesis gas, 1, and 1,4-bis(diphenylphosphino)butane.
- Zhou, Jian-Qiang,Alper, Howard
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p. 3328 - 3331
(2007/10/02)
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- A NEW AND FACILE SYNTHESIS OF N-SUBSTITUTED PYRROLIDINE OF AMINES WITH AQUEOUS SUCCINALDEHYDE USING TETRACARBONYLHYDRIDOFERRATE, HFe(CO)4(1-), AS A HIGHLY SELECTIVE REDUCING AGENT.
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Ethanolic tetracarbonylhydridoferrate combined with aqueous succinaldehyde is very efficient for the selective transformation of an amino group into a pyrrolidine ring.A large variety of both aliphatic and aromatic amines react with aqueous succinaldehyde in the presence of tetracarbonylhydridoferrate at room temperature under carbon monoxide to give the corresponding N-alkyl- and N-arylpyrrolidines in good to excellent yields.
- Shim, Sang Chul,Huh, Keun Tai,Park, Woo Hiun
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p. 259 - 264
(2007/10/02)
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- SYNTHESIS OF STERICALLY HINDERED 1-ARYLPYRROLIDINES AND 1-ARYLPIPERIDINES BY CONDENSATION OF PRIMARY AROMATIC AMINES WITH CYCLIC ETHERS OR DIOLS
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A variety of 1-(o-alkylphenyl)- and 1-(o-o'-dialkylphenyl)-pyrrolidines and -piperidines were prepared by the gas phase alumina mediated condensation of tetrahydrofuran (THF), tetrahydropyran (THP) or the corresponding diols with primary aromatic amines in fair to high yield.This methodology can also be used for the synthesis of 1-phenylhexahydroazepine from aniline.A mechanistic interpretation of the catalytic action of alumina is presented.
- Walkup, Robert E.,Searles, Scott
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p. 101 - 106
(2007/10/02)
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