- Olefin Hydroarylation Catalyzed by a Single-Component Cobalt(-I) Complex
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A single-component Co(-I) catalyst, [(PPh3)3Co(N2)]Li(THF)3, has been developed for olefin hydroarylations with (N-aryl)aryl imine substrates. More than 40 examples were examined under mild reaction conditions to afford the desired alkyl-arene product in good to excellent yields. Catalysis occurs in a regioselective manner to afford exclusively branched products with styrene-derived substrates or linear products for aliphatic olefins. Electron-withdrawing functional groups (e.g., -F, -CF3, and -CO2Me) were tolerated under the reaction conditions.
- Suslick, Benjamin A.,Tilley, T. Don
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supporting information
p. 1495 - 1499
(2021/03/03)
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- Chiral N-heterocyclic carbene-iridium complexes for asymmetric reduction of prochiral ketimines
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Enantioselective reduction of imines to the corresponding chiral secondary amines has been studied using a series of chiral half-sandwich iridium complexes. Chiral N-heterocyclic carbene (NHC) ligands in these complexes were synthesized from readily available, naturally occurring amino acids. Inexpensive phenylsilane was used as a convenient hydrogen donor. Under the optimized conditions, Ir-NHC complexes could reduce ketimines in good yields, albeit with moderate enantiomeric excess (ee). The phenylglycine derived chiral NHC was shown to give the best Ir catalyst and it also gave the maximum ee compared to catalysts prepared from other NHCs in this series. The opposite enantiomer of the reduction product was always obtained while using the Ir complex bearing a valine based NHC. The yields were consistently high with a variety of imine substrates having different steric and electronic demands.
- Kathuria, Lakshay,Samuelson, Ashoka G.
-
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- Regioselective mercury(I)/palladium(II)-catalyzed single-step approach for the synthesis of imines and 2-substituted indoles
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An efficient synthesis of ketimines was achieved through a regioselective Hg(I)-catalyzed hydroamination of terminal acetylenes in the presence of anilines. The Pd(II)-catalyzed cycliza-tion of these imines into the 2-substituted indoles was satisfactorily carried out by a C-H acti-vation. In a single-step approach, a variety of 2-substituted indoles were also generated via a Hg(I)/Pd(II)-catalyzed, one-pot, two-step process, starting from anilines and terminal acetylenes. The arylacetylenes proved to be more effective than the alkyl derivatives.
- Delgado, Francisco,Gutiérrez, Rsuini U.,Hernández-Montes, Mayra,Mendieta-Moctezuma, Aarón,Tamariz, Joaquín
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- Gold(I) complexes bearing ring-fused benzoxazine-derived triazolylidenes and their use in C–N bond-forming processes
-
We report the synthesis and full characterization of a novel series of ring-fused benzoxazine-derived triazolium salts (1a–c) and their corresponding triazolylidene gold(I) complexes (2a–c). All new compounds were fully characterized by means of 1H and 13C NMR spectroscopy, elemental analyses, and mass spectroscopy and in the case of triazoliums 1a and 1b by single-crystal X-ray diffraction. The new triazolylidene gold complexes (2a–c) were tested as precatalysts in the hydroamination and hydrohydrazination of terminal alkynes employing aniline derivatives and hydrazine as nitrogen sources, respectively.
- Campos-Dominguez, Emmanuel,Vasquez-Perez, Jose,Rojas-Lima, Susana,Lopez-Ruiz, Heraclio,Mendoza-Espinosa, Daniel
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- Syntheses of Triangular Gold Complexes and Their Applications in Hydroamination Reaction
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Triangular all-metal complexes have aroused our research interest due to their unique structural and properties. Herein, through the facile reduction of μ3-oxo complex [μ3-O(PPh3Au)3]+BF4s
- Li, Jia,Li, Xujun,Sun, Lei,Wang, Xiaoshuang,Yuan, Lixia,Wu, Lingang,Liu, Xiang,Wang, Yanlan
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supporting information
p. 4230 - 4237
(2021/09/25)
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- Synthesis and Catalytic Applications of Multinuclear Gold(I)-1,2,3-Triazolylidene Complexes
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A series of mono- to trinuclear gold(I) complexes (1–3) supported by oxo-functionalized 1,2,3-triazolylidenes have been prepared. All new compounds were fully characterized by means of 1H and 13C NMR spectroscopy, elemental analyses, and in the case of complexes 1 and 2 by x-ray diffraction. The catalytic performance of the new triazolylidene gold complexes was tested in several hydroelementation and cyclization processes employing a variety of alkynes as starting materials. According to the overall results, the trinuclear complex 3 displayed the highest catalytic activity in all processes, providing good to excellent yields under mild reaction conditions.
- Rendón-Nava, David,álvarez-Hernández, Alejandro,Mendoza-Espinosa, Daniel
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supporting information
p. 840 - 847
(2021/02/26)
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- Construction of Stable Metal–Organic Framework Platforms Embedding N-Heterocyclic Carbene Metal Complexes for Selective Catalysis
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We report a bottom-up approach to immobilize catalysts into MOFs, including copper halides and gold chloride in a predictable manner. Interestingly, the structures of MOFs bearing NHC metal complexes maintained a similar 4-fold interpenetrated cube. They
- Kim, Hyunyong,Kim, Hyunseok,Kim, Kimoon,Lee, Eunsung
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supporting information
p. 18687 - 18697
(2021/12/17)
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- Towards the rational design of ylide-substituted phosphines for gold(i)-catalysis: From inactive to ppm-level catalysis
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The implementation of gold catalysis into large-scale processes suffers from the fact that most reactions still require high catalyst loadings to achieve efficient catalysis thus making upscaling impractical. Here, we report systematic studies on the impa
- Handelmann, Jens,Babu, Chatla Naga,Steinert, Henning,Schwarz, Christopher,Scherpf, Thorsten,Kroll, Alexander,Gessner, Viktoria H.
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p. 4329 - 4337
(2021/04/12)
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- Ruthenium N-Heterocyclic Carbene Complexes for Chemoselective Reduction of Imines and Reductive Amination of Aldehydes and Ketones
-
Chemoselective reduction of imines to secondary amines is catalyzed efficiently by tethered and untethered, half-sandwich ruthenium N-heterocyclic carbene (NHC) complexes at room temperature. The untethered Ru-NHC complexes are more efficient as catalysts for the reduction of aldimines and ketimines than the tethered complexes. Using the best untethered complex as a catalyst, electronic and steric demands on the reaction was probed using a series of imines. Chemoselectivity of the catalyst towards imine reduction was tested by performing inter and intramolecular competitive reactions in a variety of ways. The catalyst exhibits a very high TON and TOF under anaerobic conditions.
- Kathuria, Lakshay,Samuelson, Ashoka G.
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supporting information
(2020/06/17)
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- Oxidative Kinetic Resolution of Acyclic Amines Based on Equilibrium Control
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An oxidative kinetic resolution of racemic acyclic amines was developed using an imine derivative as the resolving reagent and chiral phosphoric acid as the catalyst to give enantiomers in good yields with high to excellent enantioselectivities. The key t
- Akiyama, Takahiko,Ito, Yui,Miyashita, Hiromitsu,Saito, Kodai,Yamanaka, Masahiro
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supporting information
(2020/04/10)
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- Synthesis of 1,4-Benzothiazines via KI/DMSO/O2-Mediated Three-Component Oxidative Cyclization/Coupling
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A three-component transition-metal-free aerobic method for the generation of 1,4-benzothiazines is reported herein. The KI/DMSO/O2 system was found to be effective for the oxidative cyclization/coupling of 2-aminobenzenethiols, anilines, and methylketones. Hence, various structurally important imino 1,4-benzothiazines were assembled with broad functional group tolerance. Mechanistic studies revealed an initial oxidation of ketone α C?H bonds by the KI/DMSO/O2 oxidative system. (Figure presented.).
- Zhao, Jinwu,Luo, Zhigao,Xu, Jingxiu
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p. 1988 - 1992
(2020/04/29)
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- Pyridine Wingtip in [Pd(Py-tzNHC)2]2+ Complex Is a Proton Shuttle in the Catalytic Hydroamination of Alkynes
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The cationic palladium(II) complex 1 of pyridyl-mesoionic carbene ligand catalyzes Markovnikov-selective intermolecular hydroamination between anilines and terminal alkynes into the corresponding imines. The reaction proceeds at room temperature, in the a
- Virant, Miha,Mihela?, Mateja,Gazvoda, Martin,Cotman, Andrej E.,Frantar, Anja,Pinter, Balazs,Ko?mrlj, Janez
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supporting information
p. 2157 - 2161
(2020/02/13)
-
- Improving C=N bond reductions with (Cyclopentadienone)iron complexes: Scope and limitations
-
Herein, we broaden the application scope of (cyclo-pentadienone)iron complexes 1 in C=N bond reduction. The catalytic scope of pre-catalyst 1b, which is more active than the “Kn?lker complex” (1a) and other members of its family, has been expanded to the catalytic transfer hydrogenation (CTH) of a wider range of aldimines and ketimines, either pre-isolated or generated in situ. The kinetics of 1b-promoted CTH of ketimine S1 were assessed, showing a pseudo-first order profile, with TOF = 6.07 h–1 at 50 % conversion. Moreover, the chiral complex 1c and its analog 1d were employed in the enantioselective reduction of ketimines and reductive amination of ketones, giving fair to good yields and moderate enantioselectivity.
- Cettolin, Mattia,Bai, Xishan,Lübken, Dennis,Gatti, Marco,Facchini, Sofia Vailati,Piarulli, Umberto,Pignataro, Luca,Gennari, Cesare
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supporting information
p. 647 - 654
(2018/10/24)
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- Synthesis and application of axially chiral biscarbolines with functional N-O and sulfone for 1,2-transfer hydrogenations of ketimines
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A series of axially chiral biscarboline-based sulfones were synthesized from L-tryptophane and applied for enantioselective 1,2-transfer hydrogenations of ketimines using trichlorosilane. The catalyst 4e, which had a tertiary butyl group, exhibited a good conversion and high enantioselectivities up to 96%ee in the series of reactions.
- Xing, Yongfei,Wu, Shijie,Dong, Mengxian,Wang, Jie,Liu, Li,Zhu, Huajie
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supporting information
(2019/08/08)
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- 4,4′-Bipyridyl-Catalyzed Reduction of Nitroarenes by Bis(neopentylglycolato)diboron
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4,4′-Bipyridyl worked as an organocatalyst for the reduction of nitroarenes by bis(neopentylglycolato)diboron (B2nep2), followed by hydrolysis to give the corresponding anilines. This reduction proceeded under aerobic conditions without any prepurification of substrates and reagents. We found broad functional group tolerance and compatibility for O- A nd N-protecting groups under the reaction conditions. The key in this catalytic system was the addition of B2nep2 to 4,4′-bipyridyl to form N,N′-bis[(neopentylglycolato)boryl]-4,4′-bipyridinylidene as a deoxygenating reagent of nitroarenes.
- Hosoya, Hiromu,Misal Castro, Luis C.,Sultan, Ibrahim,Nakajima, Yumiko,Ohmura, Toshimichi,Sato, Kazuhiko,Tsurugi, Hayato,Suginome, Michinori,Mashima, Kazushi
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supporting information
p. 9812 - 9817
(2019/11/14)
-
- Mono- and diylide-substituted phosphines (YPhos): Impact of the ligand properties on the catalytic activity in gold(i)-catalysed hydroaminations
-
Understanding the impact of ligand properties on their performance in catalysis is seminal for future ligand design and catalyst improvement. In this work, the influence of the steric and electronic properties on the efficiency of a series of mono- and di
- Schwarz, Christopher,Handelmann, Jens,Baier, Daniel M.,Ouissa, Alina,Gessner, Viktoria H.
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p. 6808 - 6815
(2019/12/03)
-
- Efficient Synthesis of Amines by Iron-Catalyzed C=N Transfer Hydrogenation and C=O Reductive Amination
-
Here we report the catalytic transfer hydrogenation (CTH) of non-activated imines promoted by a Fe-catalyst in the absence of Lewis acid co-catalysts. Use of the (cyclopentadienone)iron complex 1, which is much more active than the classical ‘Kn?lker complex’ 2, allowed to reduce a number of N-aryl and N-alkyl imines in very good yields using iPrOH as hydrogen source. The reaction proceeds with relatively low catalyst loading (0.5–2 mol%) and, remarkably, its scope includes also ketimines, whose reduction with a Fe-complex as the only catalyst has little precedents. Based on this methodology, we developed a one-pot CTH protocol for the reductive amination of aldehydes/ketones, which provides access to secondary amines in high yield without the need to isolate imine intermediates. (Figure presented.).
- Facchini, Sofia Vailati,Cettolin, Mattia,Bai, Xishan,Casamassima, Giuseppe,Pignataro, Luca,Gennari, Cesare,Piarulli, Umberto
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supporting information
p. 1054 - 1059
(2018/01/27)
-
- Manganese-Catalyzed C?H Annulation of Ketimines with Allenes: Stereoselective Synthesis of 1-Aminoindanes
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A manganese-catalyzed C?H annulation of ketimines with poly-substituted ester-activated allenes toward the synthesis of 1-aminoindanes bearing two vicinal all-substituted carbon stereocenters and an exocyclic double bond was developed. The reaction featur
- Lei, Chong,Peng, Lijie,Ding, Ke
-
supporting information
p. 2952 - 2958
(2018/08/17)
-
- An efficient proline-based homogeneous organocatalyst with recyclability
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In this work, a homogeneous organocatalyst was developed for the asymmetric reduction of imines. This catalyst could be separated by cyclodextrin-modified Fe3O4@SiO2 magnetic nanoparticles and then released back into a fre
- Li, Qiang,Li, Yuan,Wang, Jingdong,Lin, Yingjie,Wei, Zhonglin,Duan, Haifeng,Yang, Qingbiao,Bai, Fuquan,Li, Yaoxian
-
supporting information
p. 827 - 831
(2018/02/03)
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- P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the Asymmetric Hydrogenation of N -Aryl Imines. Isolation and X-ray Analysis of Imine Iridacycles
-
A small library of Ir-MaxPHOX catalysts has been applied to the asymmetric hydrogenation of N-aryl imines. A structure-activity analysis of the three-chiral-center MaxPHOX ligand has been performed. Using complex 1b, the hydrogenation of N-aryl imines too
- Salomó, Ernest,Rojo, Pep,Hernández-Lladó, Pol,Riera, Antoni,Verdaguer, Xavier
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p. 4618 - 4627
(2018/04/26)
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- A Rhodium-Catalyzed [3 + 2] Annulation of General Aromatic Aldimines/Ketimines and N-Substituted Maleimides
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A new class of rhodium-catalyzed, C-H activation triggered [3 + 2] annulations of aromatic aldimines or ketimines and maleimides was reported in this study. A broad scope of general imines without electron-withdrawing groups were successfully activated an
- Zhu, Chengfeng,Luan, Jichao,Fang, Jun,Zhao, Xu,Wu, Xiang,Li, Yougui,Luo, Yunfei
-
supporting information
(2018/09/27)
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- A Rhodium-Catalyzed [3 + 2] Annulation of General Aromatic Aldimines/Ketimines and N-Substituted Maleimides
-
A new class of rhodium-catalyzed, C-H activation triggered [3 + 2] annulations of aromatic aldimines or ketimines and maleimides was reported in this study. A broad scope of general imines without electron-withdrawing groups were successfully activated an
- Zhu, Chengfeng,Luan, Jichao,Fang, Jun,Zhao, Xu,Wu, Xiang,Li, Yougui,Luo, Yunfei
-
supporting information
p. 5960 - 5963
(2018/09/29)
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- Thiolate-Protected Au 25 (SC 2 H 4 Ph) 18 Nanoclusters as a Catalyst for Intermolecular Hydroamination of Terminal Alkynes
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Au 25 (SC 2 H 4 Ph) 18 nanoclusters have high catalytic activity for hydroamination of terminal alkynes. This reaction proceeds under O 2 or air. The presence of molecular oxygen has a profound effect
- Nagata, Tatsuki,Adachi, Yurina,Obora, Yasushi
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p. 2655 - 2659
(2018/12/14)
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- PdII Complexes with N-(Diadamantylphosphanyl)diaminocarbene and Related Ligands: Synthesis and Catalytic Applications in Intermolecular Alkyne Hydroaminations
-
A new N-diadamantylphosphanyldiaminocarbene 5 is prepared, isolated, and characterized. The carbene appears to be much more stable than previously reported di-tert-butyl congeners. The molecular structure of the carbene is determined by X-ray diffraction
- Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Kostyuk, Aleksandr,Franco, Dario,Baron, Marco,Biffis, Andrea
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supporting information
p. 652 - 658
(2018/02/06)
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- Neutral and cationic cyclic (alkyl)(amino)carbene mercury [cAAC-Hg(ii)] complexes: Scope of hydroamination of alkynes with organomercury compounds
-
This study demonstrates the first synthesis of cyclic (alkyl)(amino)carbene (cAAC) adducts of Hg(ii), [cAACMe·HgBr(μ-Br)]2 (1a) and [cAACcy·HgBr(μ-Br)]2 (1b). Adduct 1b catalyzes intermolecular hydroamination of
- Bawari, Deependra,Goswami, Bhupendra,Sabari,Thakur, Sandeep Kumar,Varun Tej,Roy Choudhury, Angshuman,Singh, Sanjay
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supporting information
p. 6274 - 6278
(2018/05/23)
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- Ylide-Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis
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Phosphines are important ligands in homogenous catalysis and have been crucial for many advances, such as in cross-coupling, hydrofunctionalization, or hydrogenation reactions. Herein we report the synthesis and application of a novel class of phosphines bearing ylide substituents. These phosphines are easily accessible via different synthetic routes from commercially available starting materials. Owing to the extra donation from the ylide group to the phosphorus center the ligands are unusually electron-rich and can thus function as strong electron donors. The donor capacity surpasses that of commonly used phosphines and carbenes and can easily be tuned by changing the substitution pattern at the ylidic carbon atom. The huge potential of ylide-functionalized phosphines in catalysis is demonstrated by their use in gold catalysis. Excellent performance at low catalyst loadings under mild reaction conditions is thus seen in different types of transformations.
- Scherpf, Thorsten,Schwarz, Christopher,Scharf, Lennart T.,Zur, Jana-Alina,Helbig, Andreas,Gessner, Viktoria H.
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supporting information
p. 12859 - 12864
(2018/09/25)
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- Single-Step Synthesis of Dinuclear Neutral Gold(I) Complexes with Bridging Di(N-heterocyclic carbene) Ligands and Their Catalytic Performance in Cross Coupling Reactions and Alkyne Hydroamination
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We report on a single-step procedure for the synthesis of dinuclear gold(I) complexes with bridging di(N-heterocyclic carbene) (diNHC) ligands of general formula Au2Br2L1-9 (L = diNHC). The obtained complexes differ in the bridging group between the carbene donors and in the terminal wingtip substituents at the imidazol-2-ylidene rings. The complexes have been characterized by means of elemental analysis, NMR spectroscopy, ESI-MS spectrometry, and single-crystal X-ray structure analysis. The dinuclear gold(I) complexes have been tested as homogeneous catalysts in technologically relevant reactions such as the cross coupling between phenylboronic acid and aryl bromides and the intermolecular hydroamination of alkynes. The catalytic performance has been compared for complexes Au2Br2L1-9 and the benchmark mononuclear complex IPrAuCl.
- Baron, Marco,Battistel, Edoardo,Tubaro, Cristina,Biffis, Andrea,Armelao, Lidia,Rancan, Marzio,Graiff, Claudia
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p. 4213 - 4223
(2018/11/23)
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- HΒ Catalyzed Condensation Reaction Between Aromatic Ketones and Anilines: To Access Ketimines (Imines)
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Abstract: A simple approach for the formation of imines by condensation of ketones and anilines over heterogeneous catalyst (Hβ zeolite) has been successfully developed. The present catalytic system scope was explored for various aromatic ketones and anil
- Amrutham, Vasu,Mameda, Naresh,Kodumuri, Srujana,Chevella, Durgaiah,Banothu, Rammurthy,Gajula, Krishna Sai,Grigor’eva, Nellya Gennadievna,Nama, Narender
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p. 2982 - 2986
(2017/10/09)
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- Solid Supported Chiral N-Picolylimidazolidinones: Recyclable Catalysts for the Enantioselective, Metal- and Hydrogen-Free Reduction of Imines in Batch and in Flow Mode
-
A new class of solid supported chiral imidazolidinone organocatalysts for the catalytic reduction of imines with trichlorosilane has been developed. Polystyrene proved to be a more effective support than silica in terms of both chemical and stereochemical
- Porta, Riccardo,Benaglia, Maurizio,Annunziata, Rita,Puglisi, Alessandra,Celentano, Giuseppe
-
supporting information
p. 2375 - 2382
(2017/07/22)
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- Decrypting Transition States by Light: Photoisomerization as a Mechanistic Tool in Br?nsted Acid Catalysis
-
Despite the wide applicability of enantioselective Br?nsted acid catalysis, experimental insight into transition states is very rare, and most of the mechanistic knowledge is gained by theoretical calculations. Here, we present an alternative approach (de
- Renzi, Polyssena,Hioe, Johnny,Gschwind, Ruth M.
-
supporting information
p. 6752 - 6760
(2017/05/29)
-
- Palladium-catalyzed aerobic oxidative hydroamination of vinylarenes using anilines: A wacker-type amination pathway
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A palladium-catalyzed intermolecular hydroamination of vinylarene derivatives using anilines has been developed for the first time under aerobic conditions, where the regioselective formation of N-arylketimines is accomplished. The current aerobic oxidative hydroamination pathway of anilines is distinct from that of palladiumcatalyzed hydroamination reactions that proceed to give sec-arylethylamine and arylethylamine derivatives, identifying a longstanding missing reaction pathway, Wacker-type amination, to N-arylketimines using anilines. The ready availability of both starting materials, vinylarenes and anilines, offers an attractive and facile synthetic route to N-arylketimines in good to excellent yields.
- Song, Eunsun,Kim, Hun Young,Oh, Kyungsoo
-
supporting information
p. 5264 - 5267
(2017/11/06)
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- Synthesis and Catalytic Benefits of Tetranuclear Gold(I) Complexes with a C4-Symmetric Tetratriazol-5-ylidene
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The facile preparation of a C4-symmteric tetratriazolium salt and its subsequent metalation to generate a series of tetranuclear mesoionic carbene gold(I) complexes is presented. The complete structural characterization of the metallic carbenes
- Flores-Jarillo, Mariana,Mendoza-Espinosa, Daniel,Salazar-Pereda, Verónica,González-Montiel, Simplicio
-
supporting information
p. 4305 - 4312
(2017/11/20)
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- Anchoring Triazole-Gold(I) Complex into Porous Organic Polymer to Boost the Stability and Reactivity of Gold(I) Catalyst
-
Stability and reactivity have been recognized as some critical issues for gold(I) catalysts. Such issues can be well-circumvented by anchoring the gold(I) complex onto the backbones of porous organic polymer (POP) followed by coordination with a triazole ligand as illustrated in the present work via a series of gold(I)-catalyzed reactions. In this strategy, 1,2,3-triazole was used as the special "X-factor" to avoid the formation of solid AgCl involved in typical gold-activation processes. The catalyst could be readily recycled without loss of reactivity. Moreover, compared with the PPh3-modified polystyrene beads, the POP support was advantageous by providing high surface area, hierarchical porosity, and better stabilization of cations. In some cases, significantly improved reactivity was observed, even more so than using the homogeneous system, which further highlighted the great potential of this heterogeneous gold catalyst.
- Cai, Rong,Ye, Xiaohan,Sun, Qi,He, Qiuqin,He, Ying,Ma, Shengqian,Shi, Xiaodong
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p. 1087 - 1092
(2017/08/09)
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- Sulfinamide Phosphinates as Chiral Catalysts for the Enantioselective Organocatalytic Reduction of Imines
-
A new type of chiral sulfinamide phosphinate catalysts with up to three stereogenic centers, readily accessible from commercially available starting materials, is reported. The naphthyl derivative SulPhos proved to be highly efficient in the organocatalyt
- Chelouan, Ahmed,Recio, Rocío,Borrego, Lorenzo G.,álvarez, Eleuterio,Khiar, Noureddine,Fernández, Inmaculada
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supporting information
p. 3258 - 3261
(2016/07/14)
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- Copper-Catalyzed Cascade Cycloamination of α-Csp3-H Bond of N-Aryl Ketimines with Azides: Access to Quinoxalines
-
A copper-catalyzed cycloamination of α-Csp3-H bond of N-aryl ketimines with sodium azide has been developed. This methodology provides an efficient access to quinoxalines and features mild reaction conditions and readily available ketimines with diverse functional group tolerance.
- Chen, Tengfei,Chen, Xun,Wei, Jun,Lin, Dongen,Xie, Ying,Zeng, Wei
-
supporting information
p. 2078 - 2081
(2016/06/01)
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- Rh(iii)-catalyzed relay carbenoid functionalization of aromatic C-H bonds: Access to π-conjugated fused heteroarenes
-
A novel Rh(iii)-catalyzed relay cross-coupling/cyclization cascade between arylketoimines and diazoesters is described. This transformation provides a concise access to unique π-conjugated 1-azaphenalenes (1-APLEs) via a double aryl Csp2-H bond
- Xie, Ying,Chen, Xun,Liu, Xin,Su, Shi-Jian,Li, Jianzhang,Zeng, Wei
-
supporting information
p. 5856 - 5859
(2016/05/19)
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- A Frustrated Lewis Pair Catalyzed Asymmetric Transfer Hydrogenation of Imines Using Ammonia Borane
-
Inspired by the zwitterion species generated from the splitting of H2 by frustrated Lewis pairs, we put forward a novel frustrated Lewis pair by the combination of Hδ and Hδ incorporated Lewis acid and base together. Piers
- Li, Songlei,Li, Gen,Meng, Wei,Du, Haifeng
-
supporting information
p. 12956 - 12962
(2016/10/13)
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- Production of Quaternary α-Aminonitriles by Means of Indium-Catalyzed Three-Component Reaction of Alkynes, Amines, and Trimethylsilyl Cyanide
-
A novel synthesis of α-aminonitriles is described via an indium-catalyzed three-component coupling reaction of alkynes, amines, and trimethylsilyl cyanide (Me3SiCN). Hydroamination of alkynes with a subsequent nucleophilic addition of Me3
- Hamachi, Yuta,Katano, Moe,Ogiwara, Yohei,Sakai, Norio
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p. 1634 - 1637
(2016/04/26)
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- Factors influencing the photocatalytic hydroamination of alkynes with anilines catalyzed by supported gold nanoparticles under visible light irradiation
-
The addition of an N-H bond to C≡C triple bonds in the hydroamination of alkynes is of great importance in synthetic chemistry. We found that visible light irradiation can efficiently drive the direct hydroamination of alkynes using supported gold nanopar
- Zhao, Jian,Zheng, Zhanfeng,Bottle, Steven,Chen, Chao,Huang, Yiming,Sarina, Sarina,Chou, Alison,Zhu, Huaiyong
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p. 31717 - 31725
(2016/04/26)
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- Room temperature hydroamination of alkynes with anilines catalyzed by anti-Bredt di(amino)carbene gold(i) complexes
-
The room temperature hydroamination of alkynes with phenylhydrazine and anilines was achieved with an anti-Bredt di(amino) carbene gold(i) chloride as precatalyst, in the presence of KBArF as chloride scavenger. These reactions were highly regioselective and excellent conversions were obtained (up to 99%) for a series of alkynes and anilines.
- Hu, Xingbang,Martin, David,Bertrand, Guy
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p. 5993 - 5996
(2016/07/16)
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- Commercial Supported Gold Nanoparticles Catalyzed Alkyne Hydroamination and Indole Synthesis
-
Commercial gold nanoparticles supported on titanium dioxide (TiO2) were found to be a highly efficient catalyst for alkyne hydroamination. Terminal alkynes could easily undergo intermolecular hydroamination with low catalyst loadings (0.2 mol% Au) under solvent-free conditions. Indoles were efficiently synthesized using microwave heating through intramolecular hydroamination. (Figure presented.).
- Liang, Shengzong,Hammond, Luisa,Xu, Bo,Hammond, Gerald B.
-
supporting information
p. 3313 - 3318
(2016/10/21)
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- C-H activation/functionalization catalyzed by simple, well-defined low-valent cobalt complexes
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A facile C-H activation and functionalization of aromatic imines is presented using low-valent cobalt catalysts. Using Co(PMe3)4 as catalyst we have developed an efficient and simple protocol for the C-H/hydroarylation of alkynes wit
- Fallon, Brendan J.,Derat, Etienne,Amatore, Muriel,Aubert, Corinne,Chemla, Fabrice,Ferreira, Franck,Perez-Luna, Alejandro,Petit, Marc
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supporting information
p. 2448 - 2451
(2015/03/04)
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- B(C6F5)3 mediated arene hydrogenation/transannulation of para-methoxyanilines
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The stoichiometric reaction of para-methoxyanilines and B(C6F5)3 under H2 results in reduction of the N-bound phenyl ring(s), and subsequent transannular ring closure with elimination of methanol, affording the respective 7-azabicyclo[2.2.1]heptane derivatives.
- Longobardi, Lauren E.,Mahdi, Tayseer,Stephan, Douglas W.
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supporting information
p. 7114 - 7117
(2015/04/27)
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- Facile synthesis of 4- and 7-azaindoles from the corresponding imines by palladium-catalyzed cascade C-C and C-N coupling
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The cyclization of 2,3-dihalopyridines with readily available imines provides a convenient and regioselective approach to 4- and 7-azaindoles. The regioselectivity can be controlled by the choice of the halogen atoms at the pyridine ring (chlorine versus
- Pham, Ngo Nghia,Dang, Thanh Tuan,Ngo, Ngoc Thang,Villinger, Alexander,Ehlers, Peter,Langer, Peter
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supporting information
p. 6047 - 6058
(2015/06/08)
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- A Scalable Method for Regioselective 3-Acylation of 2-Substituted Indoles under Basic Conditions
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Privileged structures such as 2-arylindoles are recurrent molecular scaffolds in bioactive molecules. We here present an operationally simple, high yielding and scalable method for regioselective 3-acylation of 2-substituted indoles under basic conditions
- Johansson, Henrik,Urruticoechea, Andoni,Larsen, Inna,Sejer Pedersen, Daniel
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p. 471 - 481
(2015/08/25)
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- One-pot reductive amination of araldehydes by aniline using borohydride with CeCl3·7H2O as catalyst
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A one-pot, two-step reductive amination of araldehydes or acetophenones with anilines using NaBH4as a cheap hydride source and catalysed by CeCl3·7H2O has been achieved in EtOH at room temperature in good yields.
- Zhu, Xun,Zhou, Xiuqin,Zhang, Wei
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p. 390 - 393
(2015/08/18)
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- Ruthenium-catalyzed reductive methylation of imines using carbon dioxide and molecular hydrogen
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The use of the well-defined [Ru(triphos)(tmm)] catalyst, CO2 as C1 source, and H2 as reducing agent enabled the reductive methylation of isolated imines, as well as the direct coupling of amines with aldehydes and the subsequent reductive methylation of the insitu formed imines. The method, which afforded the corresponding N-methyl amines in very good to excellent yields, was also used for the preparation of the antifungal agent butenafine in one step with no apparent waste, thus increasing the atom efficiency of its synthesis.
- Beydoun, Kassem,Ghattas, Ghazi,Thenert, Katharina,Klankermayer, Jürgen,Leitner, Walter
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supporting information
p. 11010 - 11014
(2015/03/30)
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- Comparison of the 13C (C=N) chemical shifts of substituted N-(phenyl-ethylene)-anilines and substituted N-(benzylidene)-anilines
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Comparison of 13C NMR of C=N bond chemical shifts δC(C=N) in substituted N-(phenyl-ethylene)-anilines XArC(Me)=NArY (XPEAYs) with that in substituted N-(benzylidene)-anilines XArCH=NArY (XBAYs) was carried out. The δC(C=N)
- Cao, Zhongzhong,Cao, Chaotun,Cao, Chenzhong
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p. 564 - 569
(2015/08/03)
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- Diverse reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursors
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The reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) 1 towards metal precursors and its coordination chemistry were comprehensively studied. While the boron center in 1 is reluctant to coordinate to the alkali metals in their trifluoromethanesulfonate salts (MOTf) (M = Li, Na, K), the unprecedented compound 2 containing two L2PhB: units linked by a cyclic Li(OTf)2Li spacer was obtained from the reaction of 1 with LiOTf. Treatment of 1 with group 9 metal complexes [MCl(COD)]2 (M = Rh, Ir) afforded the first zwitterionic rhodium(i)-boronium complex 3 and the iridium(iii)-borane complex 4, respectively. The reaction pathway may involve C-H activation followed by proton migration from the metals to the boron center, demonstrating the first example of the deprotonation of metal hydrides by a basic boron. In the reactions with coinage metals, 1 could act as a two-electron reducing agent towards the metal chlorides MCl (M = Cu, Ag, Au). Meanwhile, the reaction of 1 with gold chloride supported by a N-heterocyclic carbene (NHC) produced a heteroleptic cationic gold complex [(L2PhB)Au(NHC)]Cl (6) featuring both carbene and L2PhB: ligands on the gold atom. In contrast, an isolable gold chloride complex (L2PhB)AuCl (8) was obtained by direct complexation between 1 and triphenylphosphine-gold chloride via ligand exchange. X-ray diffraction analysis and computational studies revealed the nature of the B:→Au bonding interaction in complexes 6 and 8. Natural Population Analysis (NPA) and Natural Bond Orbital (NBO) analysis support the strong σ-donating property of the L2PhB: ligand. Moreover, preliminary studies showed that complex 8 can serve as an efficient precatalyst for the addition of X-H (X = N, O, C) to alkynes under ambient conditions, demonstrating the first application of a metal complex featuring a neutral boron-based ligand in catalysis.
- Kong, Lingbing,Ganguly, Rakesh,Li, Yongxin,Kinjo, Rei
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p. 2893 - 2902
(2015/08/26)
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- Cationic zinc organyls as precatalysts for hydroamination reactions
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The cationic zinc triple-decker complex [Zn2Cp?3]+ [BArF 4]- (BArF 4=B(3,5-(CF3)2C6H3)4) exhibits catalytic acti
- Chilleck, Maren A.,Hartenstein, Larissa,Braun, Thomas,Roesky, Peter W.,Braun, Beatrice
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supporting information
p. 2594 - 2602
(2015/01/30)
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