- 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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- 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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- 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)
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- Cu/Ni-doped sulfated zirconium oxide immobilized on CdFe2O4 NPs: a cheap, sustainable and magnetically recyclable inorgano-catalyst for the efficient preparation of α-aminonitriles in aqueous media
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Abstract: A new multifunctional bimetallic nanocatalyst was prepared by immobilization of Cu/Ni-doped sulfated zirconium oxide on magnetic cadmium ferrite (CdFe2O4@SiO2@ZrO2/SO42?/Cu/Ni) and used as an efficient recyclable catalyst for one-pot as well as stepwise preparation of α-aminonitriles under mild conditions. The magnetic nanocatalyst was characterized by FTIR, TGA, VSM, XRD, EDX, FE-SEM, and TEM analyses. Also, the surface acidity of the catalyst was measured by pyridine adsorption assay. The catalyst possesses various active sites which could catalyst a variety of aromatic and aliphatic aldehydes to the corresponding α-amionitriles under moderate to high yields in the presence of aniline. Furthermore, transformation of ketones to the desired α-amionitriles and some bis-aminonitriles was also performed by this method. The catalyst could be readily recovered from the reaction mixture and reused for several times without significant loss of activity. Graphic abstract: A general and efficient method has been developed for transformation of a variety of aliphatic, aromatic aldehydes and ketones to the corresponding α-aminonitriles using a multifunctional recyclable CdFe2O4@SiO2@ZrO2/SO42?/Cu/Ni nanocatalyst.[Figure not available: see fulltext.]
- Nasseri, Mohammad Ali,Ramezani-Moghadam, Simin,Kazemnejadi, Milad,Allahresani, Ali
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p. 4233 - 4256
(2020/07/08)
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- Rhodium-Catalyzed C=N Bond Formation through a Rebound Hydrolysis Mechanism and Application in β-Lactam Synthesis
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A rhodium-catalyzed reaction of N-hydroxyanilines with diazo compounds to produce α-imino esters was developed. Distinct from the commonly accepted 1,2-H transfer for normal X-H insertion reactions, density functional theory calculations indicate that this transformation proceeds via a novel rebound hydrolysis mechanism. Furthermore, a three-component reaction was explored to synthesize highly functionalized β-lactams in good yields and diastereoselectivities.
- Chen, Long,Zhang, Linxing,Shao, Ying,Xu, Guangyang,Zhang, Xinhao,Tang, Shengbiao,Sun, Jiangtao
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supporting information
p. 4124 - 4127
(2019/06/08)
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- Photoredox Radical/Polar Crossover Enables Construction of Saturated Nitrogen Heterocycles
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Photoredox-mediated radical/polar crossover (RPC) processes offer new avenues for the synthesis of cyclic molecules. This process has been realized for the construction of medium-sized saturated nitrogen heterocycles. Photocatalytically generated alkyl ra
- Pantaine, Lo?c R.E.,Milligan, John A.,Matsui, Jennifer K.,Kelly, Christopher B.,Molander, Gary A.
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supporting information
p. 2317 - 2321
(2019/03/26)
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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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- A green and efficient hydration of alkynes catalyzed by hierarchically porous poly(ionic liquid)s solid strong acids
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The catalytic conversion of alkynes into ketones via hydration has received considerable attention, because the ketones are very important intermediates in the chemical and pharmaceutical industries. The hydration of alkynes was usually performed with rather complicated processes in presence of liquid acids or highly toxic metal catalysts. We report here a novel metal free and efficient route to conversion of alkynes into ketones catalyzed by hierarchically porous poly(ionic liquid)s solid strong acids, which were synthesized from one-step, template-free copolymerization of divinylbenzene (DVB) with nitrogen containing monomers under solvothermal condition, further by post grafting with strong acid ionic liquid groups. The porous poly(ionic liquid)s solid acids have large BET surface areas, hierarchical nanopores and enhanced acid strength. A variety of alkynes could be effectively transformed into ketones catalyzed by the synthesized porous poly(ionic liquid)s solid acids under green and mild conditions, which were much better than those of Amberlyst 15, phosphotungstic acid and sulfuric acid. Furthermore, the porous poly(ionic liquid)s solid acids also show excellent activities and good reusability in direct hydroamination of amines with phenylacetylene. This work largely expands the wide applications of porous poly(ionic liquid)s solid strong acids in hydration and hydroamination, which develops a green, efficient and cost effective approach for conversion of low cost alkynes into high-value added ketones.
- Tao, Duan-Jian,Liu, Fujian,Wang, Lin,Jiang, Lilong
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- Neutral and cationic cyclic (alkyl)(amino)carbene mercury [cAAC-Hg(ii)] complexes: Scope of hydroamination of alkynes with organomercury compounds
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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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- Synthesis of an anionic Au(I) hydroamination precatalyst supported by charged hydrido-carboranyl phosphine ligands
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Herein is reported the synthesis of an anionic gold complex bearing two charged hydrido carboranyl phosphine ligands. The compound is fully characterized by multinuclear NMR spectroscopy, high resolution mass spectrometry, as well as a single crystal X-ra
- Kleinsasser, Jack F.,Lee, Sarah E.,Lugo, Christopher A.,Tej, Varun,McArthur, Scott G.,Lavallo, Vincent
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supporting information
p. 245 - 248
(2018/10/15)
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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
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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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- 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
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supporting information
p. 827 - 831
(2018/02/03)
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- 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
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supporting information
p. 5264 - 5267
(2017/11/06)
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- Decrypting Transition States by Light: Photoisomerization as a Mechanistic Tool in Br?nsted Acid Catalysis
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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)
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- “Half-sandwich” Schiff-base Ir(III) complexes as anticancer agents
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A series of “half-sandwich” Schiff-base Ir(III) complexes were synthesized and investigated for their in vitro activities against the leukemia K562 cell line. These compounds demonstrated antiproliferative activities against K562 cells with IC50 values of 0.26–4.77 μM. In particular, compound 10c showed cytotoxicity against five cancer cell lines/sublines and stronger activities than cisplatin in K562, K562/A02, MCF-7, MCF-7/ADM, and A549 cells. Mechanism studies illustrated that compound 10c increased the level of reactive oxygen species and induced apoptosis of K562 cells. This compound effectively decreased the mitochondrial membrane potential and the protein level of Bcl-2. It also increased the protein levels of Bax, caspase-3, and caspase-9, and led to release of cytochrome c in K562 cells, indicating that the apoptosis induced by compound 10c was mediated by the intrinsic mitochondria apoptosis pathway.
- Mou, Ze-dong,Deng, Ning,Zhang, Feng,Zhang, Jiaying,Cen, Juan,Zhang, Xia
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- Hydroboration Catalyzed by 1,2,4,3-Triazaphospholenes
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The synthesis and study of the catalytic activity of 1,2,4,3-triazaphospholenes (TAPs) is reported. TAPs represent a more modular scaffold than previously reported diazaphospholenes. TAP halides were shown to catalyze the 1,2 hydroboration of 19 imines, and three α,β unsaturated aldehydes with pinacolborane, including examples that did not undergo hydroboration by previously reported diazaphospholene systems. DFT calculations support a mechanism where a triazaphospholene cation interacts with the substrate, a mechanism distinct from diazaphospholene catalyzed hydroborations.
- Tien, Chieh-Hung,Adams, Matt R.,Ferguson, Michael J.,Johnson, Erin R.,Speed, Alexander W. H.
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supporting information
p. 5565 - 5568
(2017/10/25)
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- From Ketones, Amines, and Carbon Monoxide to 4-Quinolones: Palladium-Catalyzed Oxidative Carbonylation
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A novel method of palladium-catalyzed oxidative carbonylation of ketones, amines, and carbon monoxide for the synthesis of 4-quinolones has been developed. This protocol provides a straightforward route to construct useful 4-quinolone derivatives from ine
- Wu, Jiwei,Zhou, Yuchen,Wu, Ting,Zhou, Yi,Chiang, Chien-Wei,Lei, Aiwen
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supporting information
p. 6432 - 6435
(2017/12/08)
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- Room temperature hydroamination of alkynes with anilines catalyzed by anti-Bredt di(amino)carbene gold(i) complexes
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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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- A Au(I)-Precatalyst with a Cyclopropenium Counterion: An Unusual Ion Pair
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The synthesis and X-ray crystal structure of a novel Au(I)-precatalyst applied to intermolecular alkyne hydroamination is reported. Density functional theory (DFT) calculations revealed the cyclopropenium counterion of this Au(I)-precatalyst imparts stabi
- Mir, Roya,Dudding, Travis
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p. 2675 - 2679
(2016/04/01)
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- Factors influencing the photocatalytic hydroamination of alkynes with anilines catalyzed by supported gold nanoparticles under visible light irradiation
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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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- Sulfinamide Phosphinates as Chiral Catalysts for the Enantioselective Organocatalytic Reduction of Imines
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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
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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
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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
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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
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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
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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
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supporting information
p. 12956 - 12962
(2016/10/13)
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- Construction of the 1,5-Benzodiazepine Skeleton from o-Phenylendiamine and Propargylic Alcohols via a Domino Gold-Catalyzed Hydroamination/Cyclization Process
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The gold-catalyzed reaction of o-phenylendiamine with propargylic alcohols affords 1,5-benzodiazepines bearing different substituents on the 2 and 4 positions. The method allows even for the selective preparation of 4-substituted 1,5-benzodiazepine derivatives.
- Cacchi, Sandro,Fabrizi, Giancarlo,Goggiamani, Antonella,Iazzetti, Antonia
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supporting information
p. 3511 - 3513
(2016/08/16)
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- Expanding the forefront of strong organic br?nsted acids: Proton-catalyzed hydroamination of unactivated alkenes and activation of au(i) for alkyne hydroamination
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The synthesis of a solid, bench-stable, strong organic Br?nsted acid with a computed pKa of 0.9 is reported. An X-ray crystal structure and DFT calculations are provided which offer insight into the bonding of this acid. The application of this
- Mirabdolbaghi, Roya,Dudding, Travis
-
supporting information
p. 1930 - 1933
(2015/04/27)
-
- 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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- Ethyl-Zinc(II)-Cation Equivalents: Synthesis and Hydroamination Catalysis
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Ion-like ethylzinc(II) compounds with weakly coordinating aluminates [Al(ORF)4]- and [(RFO)3Al-F-Al(ORF)3]- (RF=C(CF3)3) were synthesi
- Petersen,Tausch,Schaefer,Scherer,Roesky,Krossing
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supporting information
p. 13696 - 13702
(2015/09/22)
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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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- 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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- 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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- COMPLEXES OF PHOSPHINE LIGANDS COMPRISING A CARBA-CLOSO-DODECABORATE SUBSTITUENT
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This invention relates to complexes comprising phosphine ligands comprising a carbo-closo-dodecaborate substituent and transition metals as well as their use in catalytic reactions.
- -
-
Paragraph 0176-0180
(2014/05/24)
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- Cinchona-Derived Picolinamides: Effective Organocatalysts for Stereoselective Imine Hydrosilylation
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Picolinamide-cinchona organocatalysts for the successful enantioselective reduction of ketomines were developed. For the first time, a new type of chiral Lewis base, a cationic species, is reported to efficiently organocatalyze the addition of trichlorosi
- Barrulas, Pedro C.,Genoni, Andrea,Benaglia, Maurizio,Burke, Anthony J.
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supporting information
p. 7339 - 7342
(2016/02/20)
-
- L-Pipecolinic acid derived Lewis base organocatalyst for asymmetric reduction of N-aryl imines by trichlorosilane: Effects of the side amide group on catalytic performances
-
A series of N-formamides derived from pipecolinic acid have been synthesized and tested as Lewis base catalysts for the enantioselective reduction of N-aryl imines by trichlorosilane. Through the investigation of the structure-efficacy relationship between the side amide group and catalytic performance, several highly effective catalysts were discovered. In particular, arylamido-type catalyst 5i and non-arylamido-type catalyst 6c exhibited high reactivity and enantioselectivity, furnishing the reduction of a wide variety of N-aryl imines with high isolated yields (up to 98%) and ee values (up to 96%) under mild conditions. Moreover, these two catalysts complement each other in terms of their tolerances to nonaromatic ketimines and non-methyl ketimines. The Royal Society of Chemistry 2013.
- Wang, Zhouyu,Wang, Chao,Zhou, Li,Sun, Jian
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p. 787 - 797
(2013/02/25)
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- Highly efficient asymmetric-axle-supported N-O amides in enantioselective hydrosilylation of ketimines with trichlorosilane
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A novel asymmetric-axle-supported chiral N-O amide was synthesized and used in catalytic enantioselective hydrosilylation of N-aryl ketimines with HSiCl3 at room temperature instead of the typical -20°C. High conversion yield and high enantiose
- Pan, Wei,Deng, Yu,He, Jiang-Bo,Bai, Bing,Zhu, Hua-Jie
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p. 7253 - 7257
(2013/08/23)
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- Rhodium(III)-catalyzed hydroamination of aromatic terminal alkynes with anilines
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The dinuclear Rh(III) species [Cp*RhCl2]2 catalyzes the hydroamination reaction between an aromatic terminal alkyne (ArCCH) and an aniline (Ar′NH2), in the presence of a salt additive, to afford the ketimine Ar′N=C(Me)(Ar). A reaction pathway has been proposed on the basis of experimental and computational studies.
- Kumaran, Elumalai,Leong, Weng Kee
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experimental part
p. 1068 - 1072
(2012/04/04)
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- Room temperature tandem hydroamination and hydrosilation/protodesilation catalysis by a tricarbonylchromium-bound iridacycle
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A chromiumtricarbonyl-bound iridacycle displays novel catalytic virtues for the conversion of terminal aromatic alkynes into racemic N-phenyl, 1-arylethylamines by tandem hydro-amination and hydrosilation/protodesilation reactions under mild "one pot" con
- Iali, Wissam,Paglia, Frederic La,Pfeffer, Michel,Djukic, Jean-Pierre,Goff, Xavier-Frederic Le,Sredojevic, Dusan
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supporting information
p. 10310 - 10312,3
(2012/12/11)
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- Asymmetric hydrogenation of imines with a recyclable chiral frustrated Lewis pair catalyst
-
A camphor based chiral phosphonium hydrido borate zwitterion was synthesised and successfully applied in the enantioselective hydrogenation of imines with selectivities up to 76% ee. The high stability of the novel chiral FLP-system enables effective recy
- Ghattas, Ghazi,Chen, Dianjun,Pan, Fangfang,Klankermayer, Juergen
-
supporting information; experimental part
p. 9026 - 9028
(2012/09/08)
-
- Zinc-zinc bonded decamethyldizincocene Zn2(η5- C5Me5)2 as catalyst for the inter- and intramolecular hydroamination reaction
-
The Zn-Zn bonded compound [(η5-Cp*)2Zn 2] was investigated as catalyst for the inter- and intramolecular hydroamination reaction. High reaction rates under mild conditions were observed. This is the first application of a
- Luehl, Anja,Pada Nayek, Hari,Blechert, Siegfried,Roesky, Peter W.
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scheme or table
p. 8280 - 8282
(2011/09/14)
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- Trifluoromethanesulfonic acid as an efficient catalyst in the reduction of ketimines
-
Trifluoromethanesulfonic acid was found to be highly efficient catalyst in the reduction of ketimines with Hantzsh esters as the hydrogen source. The catalyst loading could be decreased to 1 mol %. Moderate to excellent isolated yields (up to 99 %) were obtained under mild conditions.
- Li, Jianhui,Wang, Zhouyu,Jiang, Zhenju,Jiang, Shengqian
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experimental part
p. 3101 - 3103
(2012/01/06)
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- Hydride, hydrogen, proton, and electron affinities of imines and their reaction intermediates in acetonitrile and construction of thermodynamic characteristic graphs (TCGs) of imines as a molecule ID card
-
(Chemical Equation Presented) A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C=N π-bond in the imines were estimated. The polarity of the C=N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient Molecule ID Card was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines. 2009 American Chemical Society.
- Zhu, Xiao-Qing,Liu, Qiao-Yun,Chen, Qiang,Mei, Lian-Rui
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scheme or table
p. 789 - 808
(2010/04/29)
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- Rhenium-catalyzed diastereoselective synthesis of aminoindanes via the insertion of allenes into a C-H bond
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Figure Presented. Aminoindane derivatives were synthesized diastereoselectively by the treatment of aromatic imines with allenes in the presence of a catalytic amount of a rhenium complex, [HRe(CO)4] n. The allenes inserted into the
- Kuninobu, Yoichiro,Yu, Peng,Takai, Kazuhiko
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supporting information; experimental part
p. 4274 - 4276
(2010/11/24)
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- Enantioselective hydrogenation with chiral frustrated Lewis Pairs
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No subsequent frustration: Frustrated Lewis pairs (FLPs) have been recently introduced as an unprecedented possibility to activate hydrogen. On the basis of this concept the first example of highly enantioselective catalytic hydrogenation of imines using
- Chen, Dianjun,Wang, Yutian,Klankermayer, Juergen
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supporting information; experimental part
p. 9475 - 9478
(2011/02/23)
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- Highly efficient and enantioselective iridium-catalyzed asymmetric hydrogenation of N-arylimines
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A catalytic method employing the cationic iridium-(Sc,R p)-DuanPhos [(1R,1'R,2S,2'S)-2,2'-ditert-butyl-2,2',3,3'-tetrahydro- 1H,1'H-1,1'-biisophosphindole] complex and BARF {tetrakis[3,5- bis(trifluoromethyl)phenyl]borate} counterion
- Li, Wei,Hou, Guohua,Chang, Mingxin,Zhang, Xumu
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supporting information; experimental part
p. 3123 - 3127
(2010/04/28)
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- Synthesis of bifunctional Au-Sn organic-inorganic catalysts for acid-free hydroamination reactions
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Gold(III) complexes heterogenized on the surface of a Sn-containing MCM-41 are efficient recyclable catalysts for hydroamination reactions, without requiring any acid promoters. The Royal Society of Chemistry.
- Corma, Avelino,Gonzalez-Arellano, Camino,Iglesias, Marta,Navarro, M. Teresa,Sanchez, Felix
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scheme or table
p. 6218 - 6220
(2009/05/06)
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- Development of highly enantioselective new Lewis basic N-formamide organocatalysts for hydrosilylation of imines with an unprecedented substrate profile
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l-Pipecolinic acid derived N-formamides have been developed as new Lewis basic organocatalysts that promote the asymmetric reduction of N-aryl ketimines using trichlorosilane as the reducing agent. The substituent on N4 of the piperazinyl backbone and the
- Wu, Pengcheng,Wang, Zhouyu,Cheng, Mounuo,Zhou, Li,Sun, Jian
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experimental part
p. 11304 - 11312
(2009/04/06)
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- Rationally-designed S-chiral bissulfinamides as highly enantioselective organocatalysts for reduction of ketimines
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We recently reported the first example of S-chiral organocatalysts, that are highly efficient and enantioselective in substoichometric amounts, and which use a chiral monosulfinamide group as Lewis base to activate trichlorosilane (HSiCl3) to reduce N-arylketimines. Aplausible mechanism involving two molecules of the monosulfinamde catalyst for the activation of HSiCl 3 prompted us to design S-chiral bissulfinamides as new catalysts. We herein describe our findings that an easily prepared S-chiral bissulfinamide bearing a five-methylene linkage not only inherited the excellent substrate generality from the monosulfinamide catalysts, but also exhibited further improved enantioselectivity.
- Pei, Dong,Zhang, Yu,Wei, Siyu,Wang, Meng,Sun, Jian
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supporting information; experimental part
p. 619 - 623
(2009/04/21)
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- A silver-catalyzed domino route toward 1,2-dihydroquinoline derivatives from simple anilines and alkynes
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(Chemical Equation Presented) A silver-catalyzed domino reaction of simple anilines and alkynes generates 1,2-dihydroquinoline derivatives efficiently.
- Luo, Yumei,Li, Zigang,Li, Chao-Jun
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p. 2675 - 2678
(2007/10/03)
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- Efficient ruthenium-catalyzed aerobic oxidation of amines by using a biomimetic coupled catalytic system
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Efficient aerobic oxidation of amines was developed by the use of a biomimetic coupled catalytic system involving a ruthenium-induced dehydrogenation. The principle for this aerobic oxidation is that the electron transfer from the amine to molecular oxygen occurs stepwise via coupled redox systems and this leads to a low-energy electron transfer. A substrate-selective ruthenium catalyst dehydrogenates the amine and the hydrogen atoms abstracted are transported to an electron-rich quinone (2a). The hydroquinone thus formed is subsequently reoxidized by air with the aid of an oxygen-activating [Co(salen)]-type complex (27). The reaction can be used for the preparation of ketimines and aldimines in good to high yields from the appropriate corresponding amines. The reaction proceeds with high selectivity, and the catalytic system tolerates air without being deactivated. The rate of the dehydrogenation was studied by using quinone 2a as the terminal oxidant. A catalytic cycle in which the amine promotes the dissociation of the dimeric catalyst 1 is presented.
- Samec, Joseph S. M.,Ell, Alida H.,Baeckvall, Jan-E.
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p. 2327 - 2334
(2007/10/03)
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- Dehydrogenation of aromatic amines to imines via ruthenium-catalyzed hydrogen transfer
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An efficient ruthenium-catalyzed transfer dehydrogenation of amines to imines was achieved under mild conditions using 2,6-dimethoxy benzoquinone (2) or cat. 2/MnO2 as oxidant.
- Ell, Alida H.,Samec, Joseph S. M.,Brasse, Claudia,Baeckvall, Jan-E.
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p. 1144 - 1145
(2007/10/03)
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