- Mononuclear dpp-Bian gallium complexes: Synthesis, crystal structures, and reactivity toward alkynes and enones
-
Treatment of (dpp-Bian)Ga-Ga(dpp-Bian) (1) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with iodine gives (dpp-Bian)Ga(I)-Ga(I)(dpp-Bian) (2), which reacts in situ with K(C5H4CH2CH2NMe2) (KCpDo) or K(OCH2CH2NMe2) (KORDo) to produce the monomeric species (dpp-Bian)GaCpDo (3) and (dpp-Bian)GaORDo (4), respectively. Complex 3 reacts with PhCi≡CH to give the paramagnetic derivative (dpp-Bian)Ga(Ci≡CPh)2 (5), while compound 4 is inert toward this alkyne. In contrast, monomeric (dpp-Bian)Ga(S2CNMe2) (6) reacts with PhCi≡CH and HCi≡CH to give the cycloaddition products [dpp-Bian(PhC=CH)]Ga(S2CNMe2) (7) and [dpp-Bian(HC=CH)]Ga(S2CNMe2) (8). The related compounds [dpp-Bian(MeC=CC(O)OMe)]Ga(S2CNMe2) (9) and [dpp-Bian(CH2CH=C(Me)O)]Ga(S2CNMe2) (10) have been obtained in the reactions of complex 6 with methyl 2-butynoate and methyl vinyl ketone, respectively. New complexes have been characterized by 1H NMR (3, 4, and 7-10) and ESR (5) spectroscopy; their molecular structures have been established by single-crystal X-ray analysis. The catalytic activity of complex 6 in the hydroamination and hydroarylation of alkynes has been examined.
- Fedushkin, Igor L.,Kazarina, Olga V.,Lukoyanov, Anton N.,Skatova, Alexandra A.,Bazyakina, Natalia L.,Cherkasov, Anton V.,Palamidis, Eftimios
-
-
Read Online
- Deposition of highly dispersed gold nanoparticles onto metal phosphates by deposition-precipitation with aqueous ammonia
-
An efficient method for depositing gold nanoparticles onto metal phosphate has been developed. Deposition-precipitation with aqueous ammonia enabled small gold nanoparticles to be deposited onto a series of metal phosphates with high dispersity and density. A detailed investigation of the mechanism of the formation of gold nanoparticles corroborated that strong interaction between a gold-ammine complex formed by the treatment of HAuCl4 with ammonia and positively-charged metal phosphates was responsible for the formation of highly dispersed gold nanoparticles. Furthermore, the thus-prepared gold catalysts supported on metal phosphates showed higher catalytic activity than those supported on metal oxides for the hydroamination of terminal alkynes. This journal is
- Kamata, Keigo,Miura, Hiroki,Nishio, Hidenori,Shishido, Tetsuya
-
p. 7141 - 7150
(2021/11/17)
-
- Iodine-mediated 1,2-aryl migration of primary benzhydryl amines
-
An iodine-mediated 1,2-aryl migration reaction of primary benzhydryl amines under transition metal-free conditions has been achieved. The crude imines generated by this rearrangement reaction can be directly transformed into various aromatic secondary ami
- Chang, Junbiao,Du, Yangxu,Hao, Wei,Hou, Jiao,Lu, Qing,Yu, Wenquan
-
supporting information
p. 16223 - 16226
(2021/09/22)
-
- Diethylsilane as a Powerful Reagent in Au Nanoparticle-Catalyzed Reductive Transformations
-
Diethylsilane (Et2SiH2), a simple and readily available dihydrosilane, that exhibits superior reactivity, as compared to monohydrosilanes, in a series of reductive transformations catalyzed by recyclable and reusable Au nanoparticles (1 mol-%) supported on TiO2. It reduces aldehydes or ketones almost instantaneously at ambient conditions. It can be used in a one pot rapid reductive amination procedure, in which premixing of aldehyde and amine is required prior to the addition of the reducing agent and the catalyst, even in a protic solvent. An unprecedented method for the synthesis of N-arylisoindolines is also shown in the reductive amination between o-phthalaldehyde and anilines. In this transformation, it is proposed that the intermediate N,2-diphenylisoindolin-1-imines are reduced stepwise to the isoindolines. Finally, Et2SiH2 readily reduces amides into amines in excellent yields and shorter reaction times relative to previously known analogous nano Au(0)-catalyzed protocols.
- Louka, Anastasia,Kidonakis, Marios,Saridakis, Iakovos,Zantioti-Chatzouda, Elisavet-Maria,Stratakis, Manolis
-
p. 3508 - 3514
(2020/06/02)
-
- 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
-
supporting information
p. 652 - 658
(2018/02/06)
-
- Gallium Complexes with Acenaphthene-1-Imino-2-one: Synthesis and Reactivity
-
The reduction of acenaphthene-1-(2,6-diisopropylphenyl)imino-2-one (Dpp-Mian) by gallium in the presence of iodine primarily results in a bis(ligand) paramagnetic derivative [(Dpp-Mian)2GaI] and then to a dimeric diamagnetic complex [(Dpp-Mian)
- Razborov,Lukoyanov,Moskalev,Baranov,Fedyushkin
-
p. 380 - 387
(2018/06/21)
-
- 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
-
supporting information
p. 6274 - 6278
(2018/05/23)
-
- 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
-
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
-
p. 4213 - 4223
(2018/11/23)
-
- HΒ Catalyzed Condensation Reaction Between Aromatic Ketones and Anilines: To Access Ketimines (Imines)
-
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
-
p. 2982 - 2986
(2017/10/09)
-
- “Half-sandwich” Schiff-base Ir(III) complexes as anticancer agents
-
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
-
-
- 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)
-
- 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)
-
- 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)
-
- Synthesis of Schiff bases of acetophenone with aniline and its different chloro-substituted derivatives, and study of their antioxidant, enzyme inhibitory and antimicrobial properties
-
In the present work, five different Schiff bases of acetophenone were synthesized with aniline (AL1) and its mono- and di-chloro derivatives including ortho-chloroaniline (AL2), meta-chloroaniline (AL3), para-chloroaniline (AL4), and 2,4-dichloroaniline (
- Mir, Hira,Ahmed, Dildar
-
p. 981 - 989
(2016/11/22)
-
- 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
-
p. 31717 - 31725
(2016/04/26)
-
- 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)
-
- Ruthenium-catalyzed reductive methylation of imines using carbon dioxide and molecular hydrogen
-
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
-
supporting information
p. 11010 - 11014
(2015/03/30)
-
- Comparison of the 13C (C=N) chemical shifts of substituted N-(phenyl-ethylene)-anilines and substituted N-(benzylidene)-anilines
-
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
-
p. 564 - 569
(2015/08/03)
-
- Ethyl-Zinc(II)-Cation Equivalents: Synthesis and Hydroamination Catalysis
-
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
-
supporting information
p. 13696 - 13702
(2015/09/22)
-
- Cationic zinc organyls as precatalysts for hydroamination reactions
-
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
-
supporting information
p. 2594 - 2602
(2015/01/30)
-
- Hydroamination of alkynes with aromatic amines catalyzed by digallane (dpp-bian)Ga—Ga(dpp-bian)
-
Digallane (dpp-bian)Ga—Ga(dpp-bian) (1) (dpp-bian is the 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) catalyzes the addition of 4-chloroaniline to some terminal alkynes RC≡CH (R = Bun, Ph, 4-MeC6H4). The reaction orders in each of the substrates were found for the reaction of phenylacetylene with 4-chloroaniline catalyzed by compound 1. The reaction of compound 1 with phenylacetylene in a molar ratio of 1: 10 led to 1-[N-(2,6-diisopropylphenyl)imino]-2-(1-phenylethylidene)acenaphthene (5) and the compound [C12H6(NC6H3Pr2 i)(PhC=CH2)(PhC=CH)]Ga(C≡CPh)2 (6). The reaction of digallane 1 with phenylacetylene and aniline in a stoichiometric ratio of 1: 2: 2 gave bis-anilide (dpp-bian)-Ga[N(H)Ph]2 (7) in 40% yield. The compound (PhC≡C)3Ga·THF (9) was obtained by the reaction of three equivalents of sodium phenylacetylide (prepared in situ from phenylacetylene and sodium) with one equivalent of GaCl3 in tetrahydrofuran. Compounds 5—7 and 9 were characterized by IR spectroscopy, 1H NMR spectroscopy was used to characterize products 5, 6, and 9, whereas EPR spectroscopy was used for amide 7. The structures of compounds 5—7 and 9 were determined by single crystal X-ray diffraction analysis.
- Moskalev,Skatova,Chudakova,Khvoinova,Bazyakina,Morozov,Kazarina,Cherkasov,Abakumov,Fedushkin
-
p. 2830 - 2840
(2016/09/28)
-
- Pd(II)/Bu4NBr/DMSO catalytic system for practical synthesis of indoles and pyrroles from imines through aerobic dehydrogenative cyclization
-
N-Aryl- and N-allylimines derived typically from substituted acetophenones undergo palladium(II)-catalyzed dehydrogenative cyclization reactions in the presence of tetrabutylammonium bromide and molecular oxygen in DMSO to afford indole and pyrrole deriva
- Tan, Wei Wen,Hou, Xiaoya,Yoshikai, Naohiko
-
p. 2727 - 2733
(2015/05/05)
-
- Synthesis, structure and catalytic activity of a gold(i) complex containing 1,2-bis(diphenylphosphino)benzene monoxide
-
The gold(i) complex [Au(dppbO)Cl] was synthesized by reaction of Na[AuCl4]·2H2O with 1,2-bis(diphenylphosphino)benzene (dppb) in the presence of water. This is a new method for the synthesis of a bisphosphine monoxide gold(i) complex. The new gold(i) complex was characterized by NMR spectroscopy and X-ray crystal structure analysis. In the solid state structure a relatively short contact between the oxygen atom of the phosphine oxide group and the gold center was observed. The catalytic activity of [Au(dppbO)Cl] was tested for three different intermolecular alkyne hydrofunctionalization reactions. Silver tetrafluoroborate was used as co-catalyst for halide abstraction. While the bisphosphine monoxide gold(i) complex showed moderate activity for the hydration of various alkynes and the hydroamination of phenyl acetylene, high activity was observed for the hydroarylation of ethylpropiolate. Electron-rich arenes add very fast to the C-C triple bond but with relatively low selectivity.
- Hahn, Christine,Cruz, Leticia,Villalobos, Amanda,Garza, Liliana,Adeosun, Samuel
-
p. 16300 - 16309
(2015/01/09)
-
- Simple and efficient AuI-based catalyst for hydroamination of alkynes
-
Hydroamination of terminal alkynes with anilines in the presence of (C6F5)3PAuNTf2 catalyst affords 2-aryliminoalkanes whose reduction in situ with sodium borohydride gives the corresponding secondary amines in
- Anokhin, Maksim V.,Murashkina, Arina V.,Averin, Alexei D.,Beletskaya, Irina P.
-
p. 332 - 333
(2015/02/19)
-
- 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
-
p. 787 - 797
(2013/02/25)
-
- Simple, efficient and reusable Pd-NHC catalysts for hydroamination
-
A series of chelating NHC-palladium complexes with different alkane-bridges of the type Pd[NHC-(CH2)n-NHC]X2 (X = Br or Cl, n = 2-4) were synthesized, where NHC is a triazolyl-N-heterocyclic carbene donor ligand. The bromi
- Chen, Qian,Lv, Lanlan,Yu, Meng,Shi, Yanhui,Li, Yuling,Pang, Guangsheng,Cao, Changsheng
-
p. 18359 - 18366
(2013/10/21)
-
- Palladium-catalyzed aerobic oxidative cyclization of N-aryl imines: Indole synthesis from anilines and ketones
-
We report here an operationally simple, palladium-catalyzed cyclization reaction of N-aryl imines, affording indoles via the oxidative linkage of two C-H bonds under mild conditions using molecular oxygen as the sole oxidant. The process allows quick and atom-economical assembly of indole rings from inexpensive and readily available anilines and ketones and tolerates a broad range of functional groups.
- Wei, Ye,Deb, Indubhusan,Yoshikai, Naohiko
-
supporting information; scheme or table
p. 9098 - 9101
(2012/07/14)
-
- Addition of alkynes to a gallium bis-amido complex: Imitation of transition-metal-based catalytic systems
-
Acetylene, phenylacetylene, and alkylbutynoates add reversibly to (dpp-bian)Ga-Ga(dpp-bian) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)-imino] acenaphthene) to give addition products [dpp-bian(R1C=CR 2)]Ga-Ga[(R2C=CR1/
- Fedushkin, Igor L.,Nikipelov, Alexander S.,Morozov, Alexander G.,Skatova, Alexandra A.,Cherkasov, Anton V.,Abakumov, Gleb A.
-
supporting information; experimental part
p. 255 - 266
(2012/02/16)
-
- Rhodium(III)-catalyzed hydroamination of aromatic terminal alkynes with anilines
-
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
-
experimental part
p. 1068 - 1072
(2012/04/04)
-
- Gallium trichloride catalyzed hydroamination of alkynes: Scope, limitation, and mechanistic studies by dft
-
The successful application of gallium trichloride as a catalyst for the intermolecular hydroamination of alkynes with aromatic amines is reported. The reaction is effective with many aniline derivatives and shows exclusive selectivity for the Markovnikov
- Li, Lei,Huang, Genping,Chen, Zhou,Liu, Wei,Wang, Xiufang,Chen, Yanmei,Yang, Lijuan,Li, Wu,Li, Yahong
-
supporting information
p. 5564 - 5572
(2012/11/07)
-
- Comparison of decamethyldizincocene [(η5-Cp*) 2Zn2] versus decamethylzincocene [Cp*2Zn] and diethylzinc Et2Zn as precatalysts for the intermolecular hydroamination reaction
-
A comparison of the Zn-Zn bonded species [(η5-Cp*) 2Zn2] versus the related organometallic zinc compound [Cp*2Zn] and ZnEt2 for the intermolecular hydroamination reaction in the presence of equimolar
- Luehl, Anja,Hartenstein, Larissa,Roesky, Peter W.,Blechert, Siegfried
-
p. 7109 - 7116,8
(2020/09/02)
-
- Indium catalyzed tandem hydroamination/hydroalkylation of terminal alkynes
-
The first direct intermolecular hydroamination/hydroalkylation of terminal alkynes catalyzed by In(OTf)3 under one-pot conditions leading to the formation of conjugated ketimines in good yields is described.
- Sarma, Rupam,Prajapati, Dipak
-
scheme or table
p. 9525 - 9527
(2011/10/01)
-
- 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.
-
scheme or table
p. 8280 - 8282
(2011/09/14)
-
- 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
-
scheme or table
p. 789 - 808
(2010/04/29)
-
- Highly efficient and enantioselective iridium-catalyzed asymmetric hydrogenation of N-arylimines
-
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
-
supporting information; experimental part
p. 3123 - 3127
(2010/04/28)
-
- Development of highly enantioselective new Lewis basic N-formamide organocatalysts for hydrosilylation of imines with an unprecedented substrate profile
-
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
-
experimental part
p. 11304 - 11312
(2009/04/06)
-
- Rationally-designed S-chiral bissulfinamides as highly enantioselective organocatalysts for reduction of ketimines
-
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
-
supporting information; experimental part
p. 619 - 623
(2009/04/21)
-
- Well-defined chiral spiro iridium/phosphine-oxazoline cationic complexes for highly enantioselective hydrogenation of imines at ambient pressure
-
New chiral phosphine-oxazoline ligands (7, SIPHOX) with a rigid and bulky spirobiindane scaffold were synthesized, starting with optically pure 7-diphenylphosphino-7′-trifluoromethanesulfonyloxyl-1,1′- spirobiindane, in four steps in 40-64% overall yield.
- Zhu, Shou-Fei,Xie, Jian-Bo,Zhang, Yong-Zhen,Li, Shen,Zhou, Qi-Lin
-
p. 12886 - 12891
(2008/02/05)
-
- A highly enantioselective Lewis basic organocatalyst for reduction of N-aryl imines with unprecedented substrate spectrum
-
L-Pipecolinic acid derived formamides have been developed as highly efficient and enantioselective Lewis basic organocatalysts for the reduction of N-aryl imines with trichlorosilane. Catalyst 4b afforded high isolated yields (up to 98%) and enantioselect
- Wang, Zhouyu,Ye, Xiaoxia,Wei, Siyu,Wu, Pengcheng,Zhang, Anjiang,Sun, Jian
-
p. 999 - 1001
(2007/10/03)
-
- Enantioselective hydrogenation of acyclic aromatic N-aryl imines catalyzed by an iridium complex of (S,S)-1,2-bis(tert-butylmethylphosphino)ethane
-
An iridium(I) complex of (S,S)-1,2-bis(tert-butylmethylphosphino)ethane with tetrakis(3,5-bis(trifluoromethyl)phenyl)borate as the counterion catalyzes the hydrogenation of acyclic aromatic N-aryl imines under 1 atm of hydrogen pressure at room temperatur
- Imamoto, Tsuneo,Iwadate, Noriyuki,Yoshida, Kazuhiro
-
p. 2289 - 2292
(2007/10/03)
-
- S-chiral sulfinamides as highly enantioselective organocatalysts
-
(Diagram presented) Easily accessible chiral sulfinamide 2 has been developed as the first highly efficient and enantioselective organocatalyst relying solely on a chiral sulfur center for stereochemical induction. In the presence of 20 mol % of 2, a broa
- Pei, Dong,Wang, Zhouyu,Wei, Siyu,Zhang, Yu,Sun, Jian
-
p. 5913 - 5915
(2007/10/03)
-
- Palladium catalyzed animation of vinyl chlorides: A new entry to imines, enamines and 2-amino-1,3-butadienes
-
Vinyl chlorides are employed for the first time in palladium catalyzed cross-coupling reactions with amines to furnish imines and enamines. The new methodology has been applied to the synthesis of 2-amino-1,3-butadienes, that could not be achieved from th
- Barluenga, Jose,Fernandez, M. Alejandro,Aznar, Fernando,Valdes, Carlos
-
p. 1400 - 1401
(2007/10/03)
-
- Oxidative rearrangement of ketimines to amides by MCPBA and BF3·OEt2
-
Several amides were obtained by an efficient method from the corresponding alkyl aryl ketimines in high yields. Ketimines are readily prepared from the corresponding ketones. This procedure involves the oxidation of alkyl aryl ketimines with MCPBA with BF3·OEt2. In this reaction, only aryl group of alkyl aryl ketimines was migrated to the electron deficient nitrogen atom.
- Kim, So Yeon,An, Gwang-Il,Rhee, Hakjune
-
p. 112 - 114
(2007/10/03)
-
- Thermal Cyclization of 3-Acyl-4-azidopyridines to Isoxazolo[4,3-c]pyridines
-
4-Azidopyridines such as 3-acetyl-4-azido-2-pyridones 3 or 4-azido-3-ethoxycarbonylpyridine 7 with reactive ortho-acyl substituents were obtained from the 4-hydroxy-2-pyridones 1, resp. 5 via 4-tosyloxy-2-pyridones 2 or the 2,4-dichloropyridine 6. DSC-ass
- Stadlbauer, Wolfgang,Fiala, Werner,Fischer, Michaela,Hojas, Gerhard
-
-
- Antioxidant for polyester fluids - alpha - methyl - n phenylbenzenemethanamine
-
An antioxidant for lubricating oils comprising an amine compound selected from substituted benzylamines or a substituted 1-amino-1,2,3,4-tetrahydro-naphthalene. The preferred anti-oxidants are N-(alpha -methyl -p -octylbenzyl) aniline, N-(alpha-methylbenz
- -
-
-