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Efficient reductive alkylation of aniline with acetone over Pt nanoparticles encapsulated in hollow porous carbon
Reductive alkylation of aniline with acetone over various Pt catalysts was studied under atmospheric pressure of hydrogen at room temperature. It was found that our newly designed Pt catalyst, i.e., Pt nanoparticles encapsulated in hollow porous carbon, showed excellent catalytic activity in comparison with activities of other Pt catalysts. Moreover, one-pot reductive alkylation of nitrobenzene with acetone proceeded smoothly over the catalyst. Copyright
Harada, Takashi,Ikeda, Shigeru,Okamoto, Natsumi,Ng, Yun Hau,Higashida, Suguru,Torimoto, Tsukasa,Matsumura, Michio
p. 948 - 949
(2008)
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The synthesis and structure of an amazing and stable carbonized material Cu-PC@OFM and its catalytic applications in water with mechanism explorations
An amazing and stable carbonized octahedral frame material Cu-PC@OFM was synthesized and characterized through HRTEM, SEM, XRD, XPS, and Raman spectroscopy and nitrogen adsorption/desorption analysis. In particular, the carbon matrix carrier loaded with nano-copper not only maintains the original structure, but also the nano copper particles generatedin situsignificantly improve the catalytic performance and stability. It was disclosed that the copper-based catalyst material Cu-PC@OFM showed high catalytic activity in the borrowing hydrogen reaction and the synthesis of 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives with high yields in water. This copper catalytic system provided a much greener and efficient catalyst for the synthesis of functionalized amines and 1-benzyl-2-aryl-1H-benzo[d]imidazoles with good recovery performance in water, which was the first example for the Cu-PC@OFM material-catalyzed synthesis of 1-benzyl-2-aryl-1H-benzo[d]imidazoles. In addition, a plausible reaction mechanism was proposed through some condition control experiments, deuterium labeling experiments and separation of intermediates experiments.
Tian, An-Qi,Luo, Xiang-Hao,Ren, Zhi-Lin,Zhao, Jun,Wang, Long
supporting information
p. 9614 - 9620
(2021/06/12)

Nickel?Copper bimetallic mesoporous nanoparticles: As an efficient heterogeneous catalyst for N-alkylation of amines with alcohols
A bimetallic catalyst (Ni/Cu-MCM-41) is prepared via co-condensation method. The latter is characterized by Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), diffuse reflectance spectroscopy (DRS), and nitrogen adsorption–desorption analysis. Catalytic performance of Ni/Cu-MCM-41 is probed in N-alkylation of amines with alcohols through a hydrogen autotransfer process. Noteworthy, this catalytic system appears very efficient for synthesis of a range of secondary and tertiary amines in good to excellent isolated yields. Moreover, the catalyst is successfully recovered and reused four times without notable decrease in its activity.
Nasresfahani, Zahra,Kassaee, Mohamad Z.
(2020/10/30)

CO2-tuned highly selective reduction of formamides to the corresponding methylamines
We herein describe an efficient, CO2-tuned and highly selective C-O bond cleavage of N-methylated formanilides. With easy-to-handle and commercially available NaBH4 as the reductant, a variety of formanilides could be turned into the desired tertiary amines in moderate to excellent yields. The role of CO2 has been investigated in detail, and the mechanism is proposed on the basis of experiments.
Chao, Jianbin,Guo, Zhiqiang,Pang, Tengfei,Wei, Xuehong,Xi, Chanjuan,Yan, Leilei
supporting information
p. 7534 - 7538
(2021/10/12)

Visible light-induced oxidative: N -dealkylation of alkylamines by a luminescent osmium(vi) nitrido complex
N-Dealkylation of amines by metal oxo intermediates (MO) is related to drug detoxification and DNA repair in biological systems. In this study, we report the first example of N-dealkylation of various alkylamines by a luminescent osmium(vi) nitrido complex induced by visible light. This journal is
Cheng, Shun-Cheung,Jin, Xin-Xin,Ko, Chi-Chiu,Lau, Kai-Chung,Lau, Tai-Chu,Luo, Li-Juan,Man, Wai-Lun,Pan, Yi,Peng, Min,Xiang, Jing,Yiu, Shek-Man
p. 14494 - 14498
(2021/11/17)

A Highly Dispersed Copper Nanoparticles Catalyst with a Large Number of Weak Acid Centers for Efficiently Synthesizing the High Value-Added 3-Methylindole by Aniline and Biomass-Derived Glycerin
Abstract: An excellent catalyst with a large number of weak acid centers and highly dispersed copper nanoparticles embedded in mesoporous SBA-15 carrier was successfully constructed for the purpose of efficient conversion of aniline with biomass-derived glycerin to the high value-added 3-methylindole, in which the catalyst of Cu/SBA-15 was modified with Al2O3, La2O3 and CoO in sequence. The modified carrier and the copper-based catalysts were studied by scanning electron microscopy and energy-dispersive X-ray (SEM–EDX) spectroscopy, nitrogen physical adsorption, ammonia temperature programmed desorption (NH3-TPD), hydrogen temperature programmed reduction (H2-TPR), powder X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric and differential thermal analysis (TG–DTA) and inductively coupled plasma (ICP) emission spectroscopy. The research found that the Cu/CoO/La2O3/Al2O3/SBA-15 catalyst exhibited a very good catalytic performance with 3-methylindole yield up to 73.3% and selectivity reaching 86.4%. Besides, only a 3.9% yield decreased after the catalyst was circulated seven times. The characterizations revealed that Al2O3 could enhance the polarity of the carrier, thereby the interaction between the active component and the composite carrier was strengthened and the dispersion of copper was increased significantly. Adding La2O3 to Cu/SBA-15-Al2O3 could weaken the acidity and inhibit the formation of carbon deposits. CoO promoter could increase the number of weak acid centers, which was conducive to a good dispersion of active component and the high selectivity of 3-methylindole. Furthermore, the reaction pathway of gas-phase synthesis of 3-methylindole from glycerin and aniline on Cu/CoO/La2O3/Al2O3/SBA-15 was explored. Graphic Abstract: [Figure not available: see fulltext.]
Sun, Pinghui,Lin, Shuyi,Guo, Huimei,Su, Jianhui,Shi, Lei
p. 463 - 477
(2020/07/16)

A highly efficient Co-based catalyst fabricated by coordination-assisted impregnation strategy towards tandem catalytic functionalization of nitroarenes with various alcohols
A well-defined hexamethylenetetramine (abbreviated as HMTA) based two-dimensional (2D) MOFs metalloligand (termed Zn-HMTA), with free uncoordinated tertiary amine groups, has been synthesized via solution diffusion method for the first time. The crystal structure of 2D Zn-HMTA metalloligand was determined by the single crystal X-ray diffraction (SCXRD). The SCXRD and X-ray photoelectron spectroscopy (XPS) analyses have revealed that the 2D Zn-HMTA metalloligand is rich in- free tertiary amine groups, which are of strong coordination ability to transition metal ions (e.g. Ni2+, Co2+, Zn2+, Cu2+). As a result, a 2D bimetallic Co@Zn-HMTA MOFs was synthesized via coordination-assisted impregnation (CAI) strategy attributed to the unique feature of strong coordinated ability of free tertiary amine groups. Furthermore, a series of self-supported Co-ZnO-CN nanocatalysts were afforded upon the as-synthesized Co@Zn-HMTA MOFs served as a self-sacrificial template for pyrolysis at different temperatures. The optimized catalyst (termed as Co-ZnO@CN-CAI) demonstrated the excellent catalytic performance for hydrogenation-alkylation tandem reaction in comparison with the classic ZnO@CN composite (derived from Zn-HMTA MOFs) supported metallic Co catalyst (Co-ZnO@CN-IWI) prepared by incipient wetness impregnation method. Moreover, the kinetic study was also performed to confirm that the alkylation is the rate-determining step in the hydrogenation-alkylation tandem reaction. The origin of enhanced catalytic performance of Co-ZnO@CN-CAI and the role of Co@Zn-HMTA MOFs precursor have been explored by way of various characterizations, e.g. HADDF-STEM-EDS, SEM-EDS, 13C MAS NMR, XRD, Raman and XPS, etc. It is anticipated that the prepared low-cost and easily prepared 2D Zn-HMTA metalloligand will become a general template for synthesis of highly self-supported catalysts with coordination-assisted impregnation strategy (CAI) for various catalytic reactions.
Li, Guangming,Li, Jingfang,Li, Weizuo,Li, Xuewei,Li, Zhibin,Mao, Guijie,She, Wei,Wang, Jing
p. 462 - 474
(2021/11/11)

Reductive amination of ketones/aldehydes with amines using BH3N(C2H5)3as a reductant
Herein, we report the first example of efficient reductive amination of ketones/aldehydes with amines using BH3N(C2H5)3 as a catalyst and a reductant under mild conditions, affording various tertiary and secondary amines in excellent yields. A mechanistic study indicates that BH3N(C2H5)3 plays a dual function role of promoting imine and iminium formation and serving as a reductant in reductive amination. This journal is
Zou, Qizhuang,Liu, Fei,Zhao, Tianxiang,Hu, Xingbang
supporting information
p. 8588 - 8591
(2021/09/04)

Iron-promoted dealkylative carbene aminocyclization of δ-arylamino-α-diazoesters
Herein, we report a novel methodology to accessN-aryl proline derivatives using amino-tethered α-diazoesters and cheap, readily available iron salts. Mechanistically, the aminocyclization reaction involves the initial formation of an iron-carbene complex followed by a nucleophilic attack of the aniline nitrogen atom to give an ammonium ylide intermediate, which finally undergoes the iron-promoted dealkylation.
Solé, Daniel,Amenta, Arianna,Campos, Cristina,Fernández, Israel
p. 2167 - 2176
(2021/02/26)

Synthesis method of solvent red 169
The invention belongs to the technical field of dyes, and particularly relates to a solvent red 169 synthesis method, which comprises: carrying out a reaction on bromobenzene and isopropylamine underan alkaline condition by using water as a solvent and cuprous chloride as a catalyst to obtain an intermediate N-isopropylaniline; reacting N-isopropylaniline and phthalic anhydride under the action of sulfuric acid and urotropine to obtain 1-isopropylamino anthraquinone. According to the synthesis method of the solvent red 169 provided by the invention, phthalic anhydride is used as a raw material to directly participate in dye synthesis, so that the synthesis process of anthraquinone, nitroanthraquinone and 1-chloroanthraquinone in the traditional process is omitted, the process route is greatly shortened, the discharge of wastes is greatly reduced, and the production cost is reduced.
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Paragraph 0023-0031

(2020/08/30)

Chan-Evans-Lam C?N Coupling Promoted by a Dinuclear Positively Charged Cu(II) Complex. Catalytic Performance and Some Evidence for the Mechanism of CEL Reaction Obviating Cu(III)/Cu(I) Catalytic Cycle
In the present study, we report the synthesis of a series of copper(II) complexes with a wide range of ligands and their testing in the copper catalyzed Chan-Evans-Lam (CEL) coupling of aniline and phenylboronic acid. The efficiency of the coupling was directly connected with the ease of the reduction of Cu(II) to Cu(I) of the complexes. The most efficient catalyst was derived from 4-t-butyl-2,5-bis[(quinolinylimino)methyl]phenolate and two Cu(II) ions. Depending on the counter-anion nature and the concentration of the reaction mixture, the reaction can be directed to predominant C?N-bond formation. Forty-three derivatives of diphenylamine were prepared under the optimized conditions. The proposed mechanism of the catalysis was based on the reduction potential of a series of complexes, molecular weight measurements of the catalytic complex in MeOH and the kinetic studies of aniline and phenylboronic acid coupling. In addition, an 1H NMR experiment in a sealed NMR tube, without external oxygen supply available, proved that no complete Cu(II) to Cu(I) conversion was observed under the condition, ruling out the usually accepted mechanism of the C?N coupling, which included the oxygenation of the intermediately formed Cu(I) complexes after the key step of C?N conversion had already been completed. Instead, a mechanism was proposed, involving an oxygen molecule coordinated to two copper ions in the key C?N bond formation without any detectable conversion of the Cu(II) complexes to Cu(I).
Akatyev, Nikolay,Il'in, Mikhail,Il'in, Mikhail,Peregudova, Svetlana,Peregudov, Alexander,Buyanovskaya, Anastasiya,Kudryavtsev, Kirill,Dubovik, Alexander,Grinberg, Valerij,Orlov, Victor,Pavlov, Alexander,Novikov, Valentin,Volkov, Ilya,Belokon, Yuri
p. 3010 - 3021
(2020/04/29)

Trisaminocyclopropenium Cations as Small-Molecule Organic Fluorophores: Design Guidelines and Bioimaging Applications
The discovery of fluorescence two centuries ago ushered in, what is today, an illuminating field of science rooted in the rational design of photochromic molecules for task-specific bio-, material-, and medical-driven applications. Today, this includes applications in bioimaging and diagnosis, photodynamic therapy regimes, in addition to photovoltaic devices and solar cells, among a vast multitude of other usages. In furthering this indispensable area of daily life and modern-day scientific research, we report herein the synthesis of a class of trisaminocyclopropenium fluorophores along with a systematic investigation of their unique molecular and electronic dependent photophysical properties. Among these fluorophores, tris[N(naphthalen-2-ylmethyl)phenylamino] cyclopropenium chloride (TNTPC) displayed a strong photophysical profile including a 0.92 quantum yield ascribed to intramolecular charge transfer and intramolecular through-space conjugation. Moreover, this cyclopropenium-based fluorophore functions as a competent imaging agent for DNA visualization and nuclear counterstaining in cell culture. To facilitate the broader use of these compounds, design principles supported by density functional theory calculations for engineering analogs of this class of fluorophores are offered. Collectively, this study adds to the burgeoning interest in cyclopropenium compounds and their unique properties as fluorophores with uses in bioimaging applications.
Guest, Matt,Mir, Roya,Foran, Gregory,Hickson, Brianne,Necakov, Aleksandar,Dudding, Travis
p. 13997 - 14011
(2020/12/15)

Highly Efficient and Selective N-Alkylation of Amines with Alcohols Catalyzed by in Situ Rehydrated Titanium Hydroxide
Catalytic N-alkylation of amines by alcohols to produce desired amines is an important catalytic reaction in industry. Various noble-metal-based homogeneous and heterogeneous catalysts have been reported for this process. The development of cheap non-noble-metal heterogeneous catalysts for the N-alkylation reaction would be highly desirable. Hereby, we propose the N-alkylation of amines by alcohols over a cheap and efficient heterogeneous catalyst-titanium hydroxide. This catalyst provides a selectivity higher than 90% to secondary amines for functionalized aromatic and aliphatic alcohols and amines with high catalytic activity and stability. Mild Br?nsted acidity formed by the continuous rehydration of Lewis acidity excludes the side reactions and deactivation by adsorbed species. The mechanism of the reaction involves dehydration of alcohols to ethers with subsequent C-O bond cleavage by amine with the formation of secondary amine and recovery of alcohol.
Khodakov, Andrei Y.,Kusema, Bright T.,Niu, Feng,Ordomsky, Vitaly V.,Wang, Qiyan,Yan, Zhen
p. 3404 - 3414
(2020/03/23)

COPOLYMER, PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME AND COLOR FILTER
The present invention relates to a copolymerization polymer which is derived from a compound represented by chemical formula 1 and is usable as a dye, a photosensitive resin composition comprising the copolymerization polymer as a colorant, and to a color filter manufactured by using the photosensitive resin composition. In the chemical formula 1, each substituent group is the same as defined in the specification.
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Paragraph 0637-0641

(2020/05/20)

URJC-1-MOF as New Heterogeneous Recyclable Catalyst for C-Heteroatom Coupling Reactions
Guillermo Calleja and co-workers from @urjc describe URJC-1-MOF as a new heterogeneous recyclable catalyst for c-heteroatom coupling reactions. The capacity of copper-based URJC-1-MOF as a MOF catalyst in cross-coupling reactions has been evaluated, focusing on the Chan-Lam-Evans arylation-type reactions on amines and alcohols without extra additives or ligands. The extraordinary chemical and structural stability of URJC-1-MOF and its good specific surface, make this material a promising alternative to homogeneous Cu (II) catalysts for cross-coupling reactions. URJC-1-MOF showed a remarkable catalytic activity for cross-coupling C?N and C?O reactions, higher than other heterogeneous and homogeneous copper-based catalyst, such as CuO, HKUST-1, Cu?MOF-74, Cu(OAc)2 and CuSO4?5H2O. Moreover, its easy recovery by simple filtration and reusability in successive runs without any loss of activity and stability, demonstrates the potential of URJC-1-MOF as an alternative catalyst for this kind of reactions in different chemical media of industrial interest.
Mu?oz, Antonio,Leo, Pedro,Orcajo, Gisela,Martínez, Fernando,Calleja, Guillermo
p. 3376 - 3380
(2019/07/04)

A Highly Active PN3 Manganese Pincer Complex Performing N-Alkylation of Amines under Mild Conditions
A highly active Mn(I) catalyst based on a nonsymmetric PN3-ligand scaffold for the N-alkylation of amines with alcohols utilizing the borrowing hydrogen methodology is reported. A broad range of anilines and the more challenging aliphatic amines were alkylated with primary and secondary alcohols. Moreover, the combination of low catalyst loadings and mild reaction conditions provides high efficiency for this atom-economic transformation.
Homberg, Leonard,Roller, Alexander,Hultzsch, Kai C.
supporting information

(2019/05/07)

N–Alkylation of Amines Catalyzed by a Ruthenium–Pincer Complex in the Presence of in situ Generated Sodium Alkoxide
We report the use of ruthenium–NNN-pincer complexes of the type (R2NNN)RuCl2(PPh3) (R = tBu, iPr, Cy and Ph) for the catalytic N-alkylation of primary amines under solvent-free conditions. For the first time, the base that is required to promote these reactions is generated in situ from the alcohol by the use of sodium. The resulting sodium alkoxide regenerates the alcohol substrate while acting as the water scavenger thus mitigating the need of an additional base. Among the catalysts screened, (tBu2NNN)RuCl2(PPh3) (0.02 mol-%) gives very high turnovers and good yields at 140 °C. The (tBu2NNN)RuCl2(PPh3) catalyzed N-alkylation tolerates a variety of amine and alcohol substrates. While excellent turnover (29000) was obtained for the (tBu2NNN)RuCl2(PPh3) (0.002 mol-%) catalyzed alkylation of aniline with cyclohexyl methanol, the turnovers obtained in the corresponding catalytic methylation of p-anisidine was also very high (12000). The (tBu2NNN)RuCl2(PPh3) catalyzed reactions have also been accomplished under open-vessel conditions resulting in a net dehydrogenative coupling reaction. This protocol has been used to transform benzene-1,2-diamines to benzimidazoles with high productivity (12000 turnovers). DFT studies indicate that while β-hydride elimination is rate-determining (RDTS: 24.31 kcal/mol) for the alcohol dehydrogenation segment which is endothermic, insertion of the imine is rate-determining (RDTS: 11.26 kcal/mol) for its hydrogenation that is exothermic.
Das, Kanu,Nandi, Pran Gobinda,Islam, Khadimul,Srivastava, Hemant Kumar,Kumar, Akshai
p. 6855 - 6866
(2019/11/03)

Hydrogenation and: N-Alkylation of anilines and imines via transfer hydrogenation with homogeneous nickel compounds
The nickel-catalyzed N-Alkylation of a variety of arylamines via transfer hydrogenation in the absence of pressurized hydrogen and basic or acidic additives was achieved in a tandem reaction. This process was further extended to the CN bond reduction and N-Alkylation of a variety of imines with ethanol, the latter acting as a hydrogen and acetaldehyde source, which allowed for the reduction and subsequent condensation to yield the corresponding N-Alkylated products.
Benitez-Medina, G. Eliad,García, Juventino J.
supporting information
p. 17579 - 17587
(2019/12/23)

Sodium Triethylborohydride-Catalyzed Controlled Reduction of Unactivated Amides to Secondary or Tertiary Amines
The first transition-metal-free catalytic protocol for controlled reduction of amide functions using cheap and bench-stable hydrosilanes as reducing agents has been established. By altering the hydrosilane and solvent, the new method enables the selective cleavage of unactivated C-O bonds in amides and allows the C-N bonds to selectively break via the deacylated cleavage. Overall, this novel process may offer a versatile alternative to current methodologies employing stoichiometric metal systems for the controlled reduction of carboxamides.
Yao, Wubing,He, Lili,Han, Deman,Zhong, Aiguo
(2019/11/14)

Sodium Triethylborohydride-Catalyzed Controlled Reduction of Unactivated Amides to Secondary or Tertiary Amines
The first transition-metal-free catalytic protocol for controlled reduction of amide functions using cheap and bench-stable hydrosilanes as reducing agents has been established. By altering the hydrosilane and solvent, the new method enables the selective cleavage of unactivated C-O bonds in amides and allows the C-N bonds to selectively break via the deacylated cleavage. Overall, this novel process may offer a versatile alternative to current methodologies employing stoichiometric metal systems for the controlled reduction of carboxamides.
Yao, Wubing,He, Lili,Han, Deman,Zhong, Aiguo
p. 14627 - 14635
(2019/12/02)

Anti-1,2,2,3,4,4-hexamethylphosphetane 1-oxide
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Nykaza, Trevor V.,Cooper, Julian C.,Radosevich, Alexander T.
p. 418 - 435
(2019/11/21)

Catalyst-Free Reductive Coupling of Aromatic and Aliphatic Nitro Compounds with Organohalides
A rare reductive coupling of nitro compounds with organohalides has been realized. The reaction is initiated by a partial reduction of the nitro group to a nitrenoid intermediate. Therefore, not only aromatic but also aliphatic nitro compounds are efficiently transformed into monoalkylated amines, with organohalides as the alkylating agent. Given the innate reactivity of the nitrenoid, a catalyst is not required, resulting in a high tolerance for aryl halide substituents in both starting materials.
Rauser, Marian,Eckert, Raphael,Gerbershagen, Max,Niggemann, Meike
supporting information
p. 6713 - 6717
(2019/04/14)

An Efficient Metal-Free Method for the Denitrosation of Aryl N-Nitrosamines at Room Temperature
A simple and practical method for the denitrosation of aryl N-nitrosamines to secondary amines is reported under metal-free conditions using iodine and triethylsilane. Several reduction-susceptible functional groups such as alkene, alkyne, nitrile, nitro, aldehyde, ketone and ester were found to be very stable during the denitrosation, which is remarkable. Broad substrate scope, room temperature reactions and excellent yields are the additional features of the current methodology. (Figure presented.).
Chaudhary, Priyanka,Korde, Rishi,Gupta, Surabhi,Sureshbabu, Popuri,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
supporting information
p. 556 - 561
(2017/11/13)

CLEAVABLE TETRAZINE USED IN BIO-ORTHOGONAL DRUG ACTIVATION
Disclosed is an advancement in provoked chemical cleavage. Thereby the invention provides the use of a diene as a chemically cleavable group attached to a Construct, and the use of a dienophile to provoke the release of the Construct by allowing the diene to react with a dienophile capable of undergoing an inverse electron demand Diels Alder reaction with the diene. The invention includes a kit for releasing a Construct CA bound to a Trigger TR, the kit comprising a tetrazine and a dienophile, wherein the Trigger is the tetrazine. The invention also includes the use of the formation of a pyridazine by reacting a tetrazine comprising a Construct CA bound thereto and a dienophile, as a chemical tool for the release, in a chemical, biological or physiological environment, of said Construct.
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Page/Page column 176-179

(2018/02/03)

N-Alkylation of Aniline and Its Derivatives by Alcohols in the Presence of Copper Compounds
N-Alkyl- and N,N-dialkyl-substituted anilines were obtained in the reaction of aniline and its derivatives with primary and secondary alcohols in the presence of catalysts CuCl2·2H2O, CuBr2 and halomethanes as promoters.
Bayguzina,Musina, Ch. F.,Khusnutdinov
p. 1652 - 1659
(2019/02/12)

Intermolecular Reductive C-N Cross Coupling of Nitroarenes and Boronic Acids by PIII/PV=O Catalysis
A main group-catalyzed method for the synthesis of aryl- and heteroarylamines by intermolecular C-N coupling is reported. The method employs a small-ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane) and a terminal hydrosilane reductant (phenylsilane) to drive reductive intermolecular coupling of nitro(hetero)arenes with boronic acids. Applications to the construction of both Csp2-N (from arylboronic acids) and Csp3-N bonds (from alkylboronic acids) are demonstrated; the reaction is stereospecific with respect to Csp3-N bond formation. The method constitutes a new route from readily available building blocks to valuable nitrogen-containing products with complementarity in both scope and chemoselectivity to existing catalytic C-N coupling methods.
Nykaza, Trevor V.,Cooper, Julian C.,Li, Gen,Mahieu, Nolwenn,Ramirez, Antonio,Luzung, Michael R.,Radosevich, Alexander T.
supporting information
p. 15200 - 15205
(2018/11/30)

Reductive Amination by Photoredox Catalysis and Polarity-Matched Hydrogen Atom Transfer
The excitation of a RuII photosensitizer in the presence of ascorbic acid leads to the reduction of iminium ions to electron-rich α-aminoalkyl radical intermediates, which are rapidly converted into reductive amination products by thiol-mediated hydrogen atom transfer (HAT). As a result, the reductive amination of carbonyl compounds with amines by photoredox catalysis proceeds in good to excellent yields and with broad substrate scope and good functional group tolerance. The three key features of this work are 1) the rapid interception of electron-rich α-aminoalkyl radical intermediates by polarity-matched HAT in a photoredox reaction, 2) the method of reductive amination by photoredox catalysis itself, and 3) the application of this new method for temporally and spatially controlled reactions on a solid support, as demonstrated by the attachment of a fluorescent dye on an activated cellulose support by photoredox-catalyzed reductive amination.
Guo, Xingwei,Wenger, Oliver S.
supporting information
p. 2469 - 2473
(2018/01/27)

Direct Reductive Amination of Carbonyl Compounds Catalyzed by a Moisture Tolerant Tin(IV) Lewis Acid
Despite the ever-broadening applications of main-group ‘frustrated Lewis pair’ (FLP) chemistry to both new and established reactions, their typical intolerance of water, especially at elevated temperatures (>100 °C), represents a key barrier to their mainstream adoption. Herein we report that FLPs based on the Lewis acid iPr3SnOTf are moisture tolerant in the presence of moderately strong nitrogenous bases, even under high temperature regimes, allowing them to operate as simple and effective catalysts for the reductive amination of organic carbonyls, including for challenging bulky amine and carbonyl substrate partners. (Figure presented.).
Sapsford, Joshua S.,Scott, Daniel J.,Allcock, Nathan J.,Fuchter, Matthew J.,Tighe, Christopher J.,Ashley, Andrew E.
supporting information
p. 1066 - 1071
(2018/01/27)

Sulfonato-diketimine Copper(II) Complexes: Synthesis and Application as Catalysts in Chan-Evans-Lam Couplings
Copper complexes bearing a diketimino-sulfonate ligand, LCu(NO3)(NCMe), were prepared and proved to be stable to water for several hours in solution. Prolonged standing in the presence of water or strong bases led to desulfonation of the ligand. LCu(NO3) was inactive in the polymerization of lactide (in the presence of benzyl alcohol), but showed high activity for the Chan-Evans-Lam coupling of a variety of amines and anilines. Couplings do not require addition of base, ligand, or molecular sieves. Mechanistic investigations indicate a catalytic cycle involving dioxygen as the required oxidant, precoordination of boronic acid to the sulfonate group, and transmetalation occurring prior to reaction with the nucleophile.
Hardouin Duparc, Valérie,Schaper, Frank
supporting information
p. 3053 - 3060
(2017/09/05)

Novel nonmetal catalytic bidirectional selective reduction method of tertiary aromatic amide
The invention relates to a novel effective bidirectional selective environment-friendly method for hydrosilation reduction of tertiary aromatic amide and an organic silicon reagent. The method comprises the following steps: selecting a nonmetal catalytic system, and selectively preparing a secondary or tertiary organic amine compound by successively catalyzing tertiary aromatic amide and cheap PHMS or triethoxysilane under a mild condition. By adopting the method, the bidirectional selective reduction of the tertiary aromatic amide is realized by innovatively utilizing an electronic effect and steric hindrance difference of an organic silicon reagent at first time, so that a brand new strategy is provided for the reduction of amide and derivative of the amide, the defects of the traditional method that the substrate functional group is poor in compatibility, the production cost is high and the like can be overcome, and the application prospect of the amine compound prepared in industrial production or laboratory is promising.
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Paragraph 0066; 0067; 0068; 0069

(2017/10/22)

General Reductive Amination of Aldehydes and Ketones with Amines and Nitroaromatics under H2 by Recyclable Iridium Catalysts
Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaromatics and amines using H2. The iridium catalysts were prepared by pyrolysis of ionic liquid 1-methyl-3-cyanomethylimidazoulium chloride ([MCNI]Cl) with iridium chloride (IrCl3) in activated carbons. Iridium particles were well dispersed and stable in the N-doped carbon materials from [MCNI]Cl with activated carbon. The Ir@NC(600-2h) catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H2 and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC(600-2h) catalyst can be reusable several times without evident deactivation.
Sui, Dejun,Mao, Fei,Fan, Haipeng,Qi, Zhengliang,Huang, Jun
supporting information
p. 1371 - 137
(2017/10/05)

Synthesis of β-Lactams by Palladium(0)-Catalyzed C(sp3)?H Carbamoylation
A general and user-friendly synthesis of β-lactams is reported that makes use of Pd0-catalyzed carbamoylation of C(sp3)?H bonds, and operates under stoichiometric carbon monoxide in a two-chamber reactor. This reaction is compatible with a range of primary, secondary and activated tertiary C?H bonds, in contrast to previous methods based on C(sp3)?H activation. In addition, the feasibility of an enantioselective version using a chiral phosphonite ligand is demonstrated. Finally, this method can be employed to synthesize valuable enantiopure free β-lactams and β-amino acids.
Dailler, David,Rocaboy, Ronan,Baudoin, Olivier
supporting information
p. 7218 - 7222
(2017/06/13)

Formation of Phenyliodonio-Substituted Spirofurooxindole Trifluoroacetates from N-Substituted 3-Oxopentanediamides via Phenyliodine Bis(trifluoroacetate)-Mediated Oxidative Cascade Reactions
The reaction of N-substituted 3-oxopentanediamides with phenyliodine bis(trifluoroacetate) (PIFA) was found to give a novel class of phenyliodonio-substituted spirofurooxindole trifluoroacetates under metal-free conditions. The reaction is postulated to proceed via a cascade process involving an oxidative C—O bond formation, an oxidative C—C bond formation and a final iodination step. (Figure presented.).
Hu, Bei,Cao, Yang,Zhang, Bobo,Zhang-Negrerie, Daisy,Du, Yunfei
supporting information
p. 2542 - 2548
(2017/08/16)

Transition Metal-Catalysed Intramolecular Carbenoid C?H Insertion for Pyrrolidine Formation by Decomposition of α-Diazoesters
The use of Pd-, Rh(II)- and Ru(II)-based catalysts has been explored in the transition metal-catalysed intramolecular carbenoid C?H insertion of α-diazoesters leading to pyrrolidines. Although the outcome of the reaction was highly substrate-dependent, in general, it was possible to control the chemoselectivity of the process towards pyrrolidines by adequate catalyst selection. The Pd(0)-catalysts were as efficient as [Rh(Ph3CCO2)2]2 in promoting the C(sp3)?H insertion of ortho-substituted anilines. In contrast, for anilines bearing meta- and para-substituents, the Rh(II)-catalyst provided the best chemoselectivities and reaction yields. On the other hand, [Ru(p-cymene)Cl2]2 was the most efficient catalyst for the insertion reaction of the N-benzyl-N-phenyl and N,N-dibenzyl α-diazoesters, while the C(sp3)?H insertion of the N-benzylsulfonamide substrate was only promoted by [Rh(Ph3CCO2)2]2. According to density functional theory (DFT) calculations, the mechanism involved in the Pd(0)- and Ru(II)-catalysed C(sp3)?H insertions differs considerably from that typically proposed for the Rh(II)-catalysed transformation. Whereas the Pd(0)-catalysed reaction involves a Pd-mediated 1,5-H migration from the C(sp3)?H bond to the carbenoid carbon atom leading to the formal oxidation of the transition metal, a Ru(II)-promoted Mannich type reaction involving a zwitterionic intermediate seems to be operative in the Ru(II)-catalysed transformation. (Figure presented.).
Solé, Daniel,Amenta, Arianna,Mariani, Francesco,Bennasar, M.-Llu?sa,Fernández, Israel
supporting information
p. 3654 - 3664
(2017/09/13)

REACTIONS OF STANNYL CATIONS
The present invention relates to a method of reducing, cleaving and/or coupling at least one C=O, C-O, C=C or C=N bond of a compound, using a reagent comprising a stannyl cation.
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Page/Page column 22; 23

(2018/01/17)

Scalable synthesis of secondary and tertiary amines by heterogeneous Pt-Sn/γ-Al2O3catalyzed N-alkylation of amines with alcohols
Synthesis of secondary and tertiary amines has been efficiently realized from the N-alkylation of amines with alcohols by means of heterogeneous bimetallic Pt-Sn/γ-Al2O3catalyst (0.5?wt % Pt, molar ratio Pt:Sn?=?1:3) through a borrowing hydrogen strategy. The Pt-Sn/γ-Al2O3catalyst has exhibited very high catalytic activity towards a wide range of amines and alcohols, and can be conveniently recycled without Pt metal leaching. The present protocol was applied for the synthesis of N-phenylbenzylamine in 96% isolated yield from aniline and benzyl alcohol on a 2.1?kg scale of the substrates, demonstrating its potential applicability for higher-order amine synthesis.
Wu, Kaikai,He, Wei,Sun, Chenglin,Yu, Zhengkun
supporting information
p. 8516 - 8521
(2016/11/28)

Unsupported Nanoporous Gold Catalyst for Chemoselective Hydrogenation Reactions under Low Pressure: Effect of Residual Silver on the Reaction
For the first time, H-H dissociation on an unsupported nanoporous gold (AuNPore) surface is reported for chemoselective hydrogenation of C=C, C=C, C=N, and C=O bonds under mild conditions (8 atm H2 pressure, 90 °C). Silver doping in AuNPore, which was inevitable for its preparation through a process of dealloying of Au-Ag alloy, exhibited a remarkable difference in catalytic activity between two catalysts, Au>99Ag1NPore and Au90Ag10NPore.The former was more active and the latter less active in H2 hydrogenation, while the reverse tendency was observed for O2 oxidation. This marked contrast between H2 reduction and O2 oxidation is discussed. Further, Au>99Ag1NPore showed a high chemoselectivity toward reduction of terminal alkynes in the presence of internal alkynes which was not achieved using supported gold nanoparticle catalysts and other previously known methods. Reductive amination, which has great significance in synthesis of amines due to its atom-economical nature, was also realized using Au>99Ag1NPore, and the Au>99Ag1NPore/H2 system showed a preference for the reduction of aldehydes in the presence of imines. In addition to this high chemoselectivity, easy recovery and high reusability of AuNPore make it a promising heterogeneous catalyst for hydrogenation reactions.
Takale, Balaram S.,Feng, Xiujuan,Lu, Ye,Bao, Ming,Jin, Tienan,Minato, Taketoshi,Yamamoto, Yoshinori
p. 10356 - 10364
(2016/08/31)

Chan-Evans-Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem
The Chan-Evans-Lam reaction is a valuable C-N bond forming process. However, aryl boronic acid pinacol (BPin) ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. Herein, we report effective reaction conditions for the Chan-Evans-Lam amination of aryl BPin with alkyl and aryl amines. A mixed MeCN/EtOH solvent system was found to enable effective C-N bond formation using aryl amines while EtOH is not required for the coupling of alkyl amines.
Vantourout, Julien C.,Law, Robert P.,Isidro-Llobet, Albert,Atkinson, Stephen J.,Watson, Allan J. B.
p. 3942 - 3950
(2016/05/24)

Heterogeneous cobalt catalysts for reductive amination with H2: General synthesis of secondary and tertiary amines
Heterogeneous Co@NC catalysts were prepared, characterized and applied for the reductive amination of aldehydes and ketones with H2 gas. The Co catalyst Co@NC (800-2 h) was found to be active and selective for the reductive amination of aldehydes and ketones using H2 gas. Thus, general synthesis of secondary and tertiary amines was developed by the Co-catalyzed reductive amination with H2 gas, and various secondary and tertiary amines can be obtained in high yields. Moreover, a practical synthesis of N-substituted isoindolinones was also presented by a one step process with the Co@NC (800-2 h) catalyst. The Co@NC (800-2 h) catalyst is reusable at least five times without evident loss of activity.
Mao, Fei,Sui, Dejun,Qi, Zhengliang,Fan, Haipeng,Chen, Rizhi,Huang, Jun
p. 94068 - 94073
(2016/10/22)

Nickel(II) complex covalently anchored on core shell structured SiO2@Fe3O4 nanoparticles: A robust and magnetically retrievable catalyst for direct one-pot reductive amination of ketones
A robust and efficient core shell structured magnetically retrievable nickel nanocatalytic system was fabricated via the covalent immobilization of 2-acetyl furan on the surface of an amine functionalized silica coated magnetic nanosupport followed by its metallation with nickel acetate. The newly synthesized magnetic silica based organic-inorganic hybrid nanocatalyst (Ni-ACF@Am-SiO2@Fe3O4) was systematically affirmed using several physico-chemical characterization tools such as FT-IR, XRD, VSM, SEM, TEM, EDS, ED-XRF and AAS. Thereafter, the catalytic performance of this Ni-ACF@Am-SiO2@Fe3O4 nanocatalyst was investigated in the one-pot reductive amination of ketones using NaBH4 as the reductant under neat conditions. The developed core shell magnetic silica based nickel nanocatalyst successfully afforded a structurally diverse range of secondary amines with high turnover frequency (TOF) and excellent conversion percentage. Additionally, it was found that this catalyst could not only be retrieved from the reaction vessel within a fraction of seconds using an external magnet but also be recycled for multiple runs without any discernible loss in its activity that rendered this protocol superior to all the previously established methodologies for the one-pot synthesis of substituted amines. Besides, some of the other fascinating features of this methodology that made it a potential candidate for addressing various economic and environmental concerns were ambient reaction conditions, broad substrate scope, simple workup procedure, shorter reaction time and cost effectiveness.
Sharma, Rakesh Kumar,Dutta, Sriparna,Sharma, Shivani
p. 2089 - 2101
(2016/03/19)

B(C6F5)3-Catalyzed Reductive Amination using Hydrosilanes
In contrast to the established dogma that B(C6F5)3 is irreversibly poisoned by excess H2O/amine (or imine) bases, B(C6F5)3 is actually a water-tolerant catalyst for the reductive amination of primary and secondary arylamines with aldehydes and ketones in "wet solvents" at raised temperatures and using only 1.2 equiv of Me2PhSiH as reductant. Arylamines/N-arylimines do not result in the irreversible deprotonation of H2O-B(C6F5)3, allowing sufficient B(C6F5)3 to be evolved at raised temperatures to effect catalytic reductions. Stronger Br?nsted basic amines such as tBuNH2 (and derived imines) result in irreversible formation of [HO-B(C6F5)3]- from H2O-B(C6F5)3, precluding the formation of B(C6F5)3 at raised temperatures and thus preventing any imine reduction. A substrate scope exploration using 1 mol % nonpurified B(C6F5)3 and "wet solvents" demonstrates that this is an operationally simple and effective methodology for the production of secondary and tertiary arylamines in high yield, with imine reduction proceeding in preference to other possible reactions catalyzed by B(C6F5)3, including the dehydrosilylation of H2O and the reduction of carbonyl moieties (e.g., esters).
Fasano, Valerio,Radcliffe, James E.,Ingleson, Michael J.
p. 1793 - 1798
(2016/03/15)

Thioimidazoline based compounds reverse glucocorticoid resistance in human acute lymphoblastic leukemia xenografts
Glucocorticoids form a critical component of chemotherapy regimens for pediatric acute lymphoblastic leukemia (ALL) and the initial response to glucocorticoid therapy is a major prognostic factor, where resistance is predictive of poor outcome. A high-throughput screen identified four thioimidazoline-containing compounds that reversed dexamethasone resistance in an ALL xenograft derived from a chemoresistant pediatric ALL. The lead compound (1) was synergistic when used in combination with the glucocorticoids, dexamethasone or prednisolone. Synergy was observed in a range of dexamethasone-resistant xenografts representative of B-cell precursor ALL (BCP-ALL) and T-cell ALL. We describe here the synthesis of twenty compounds and biological evaluation of thirty two molecules that explore the structure-activity relationships (SAR) of this novel class of glucocorticoid sensitizing compounds. SAR analysis has identified that the most effective dexamethasone sensitizers contain a thioimidazoline acetamide substructure with a large hydrophobic moiety on the acetamide. This journal is
Toscan, Cara E.,Rahimi, Marwa,Bhadbhade, Mohan,Pickford, Russell,McAlpine, Shelli R.,Lock, Richard B.
p. 6299 - 6312
(2015/06/08)

Supported gold-palladium alloy nanoparticle catalyzed tandem oxidation routes to N-substituted anilines from non-aromatic compounds
In the presence of a supported gold-palladium alloy nanoparticle catalyst (Au-Pd/Al2O3), various kinds of N-substituted anilines can be synthesized from non-aromatic compounds. The observed catalysis is truly heterogeneous, and Au-Pd/Al2O3 can be reused without a significant loss of its catalytic performance.
Taniguchi, Kento,Jin, Xiongjie,Yamaguchi, Kazuya,Mizuno, Noritaka
supporting information
p. 14969 - 14972
(2015/10/12)

Facile and efficient reductive N-alkylation of nitrobenzenes with alcohols catalyzed by Cu-Cr/γ-Al2O3
A facile and efficient method for reductive N-alkylation of nitrobenzenes with alcohols catalyzed by the bimetallic catalyst Cu30Cr5/γ-Al2O3, in a fixed-bed reactor, was successfully established. X-ray diffraction, temperature-programmed reduction, and X-ray photoelectron spectroscopy were used to characterize the catalyst. Introduction of Cr to Cu30/γ-Al2O3 was found to substantially enhance the dispersion of Cu0 particles, which are believed to be the active sites for the reductive N-alkylation. The reaction conditions were optimized and a series of alcohols and nitrobenzenes were converted into N-alkylated anilines in more than 90 % yield by use of this catalyst.
Song, Ge,Tian, Jun,Chen, Ligong,Li, Yang
p. 5399 - 5409
(2015/07/08)

Alkylation of Amines with Alcohols and Amines by a Single Catalyst under Mild Conditions
An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N-methylated products selectively. A strong solvent effect is observed for the reaction.
Zou, Qingzhu,Wang, Chao,Smith, Jen,Xue, Dong,Xiao, Jianliang
supporting information
p. 9656 - 9661
(2015/06/30)

Cu-catalyzed oxidative Povarov reactions between N-alkyl N-methylanilines and saturated oxa- and thiacycles
Cu-catalyzed oxidative Povarov reactions between N,N-dialkylanilines and saturated oxa- or thiacycles with tert-butyl hydroperoxide (TBHP) are described; notably, the reactions use neither [4π] nor [2π]-motifs as the initial reagents. The use of cheap alkane-based substances as building units is of mechanistic and practical interest as two inert sp3 C-H bonds are activated.
Kawade, Rahul Kisan,Huple, Deepak B.,Lin, Rong-Jing,Liu, Rai-Shung
supporting information
p. 6625 - 6628
(2015/04/14)

A further decrease in the catalyst loading for the palladium-catalyzed direct intramolecular arylation of amides and sulfonamides
The direct arylation of N-substituted o-bromobenzanilides and benzenesulfonamides via C-H bond functionalization has been developed using very low catalyst loadings. This novel cost-effective and more sustainable method relies on a PCN-type palladium pincer complex as a highly active palladium source, providing a general and efficient access to phenanthridinones, biaryl sultams and related heterocyclic systems. The beneficial effect of water as cosolvent has been observed in this process, which is not seriously influenced by electronic effects at the arene moieties or sterically demanding substituents at the amide or sulfonamide nitrogen. In addition, a number of experiments (kinetic plot, poisoning assays, TEM, ESI) have been performed in order to understand the role of the employed palladium complex in this reaction.
Conde, Nerea,Churruca, Fátima,Sanmartin, Raul,Herrero, María Teresa,Domínguez, Esther
supporting information
p. 1525 - 1531
(2015/05/26)

Higher-Affinity Agonists of 5-HT1AR Discovered through Tuning the Binding-Site Flexibility
Discovery of high-affinity and high-selectivity agonists of 5-HT1AR has become very attractive due to their potential therapeutic effects on multiple 5-HT1AR-related psychological and neurological problems. On the basis of our previously designed lead compound FW01 (Ki = 51.9 nM, denoted as 9a in the present study), we performed large-scale molecular dynamics simulations and molecular docking operations on 5-HT1AR-9a binding. We found the flip-packing events for the headgroup of 9a, and we also found that its tail group could bind flexibly at the agonist-binding site of 5-HT1AR. By finely tuning the flip-packing phenomenon of the 9a headgroup and tuning the binding flexibility of 9a tail group, we virtually designed a series of new 9a derivatives through molecular docking operations and first-principles calculations and predicted that these newly designed 9a derivatives should be higher-affinity agonists of 5-HT1AR. The computational predictions on the new 9a derivatives have been confirmed by our wet-experimental studies as chemical synthesis, binding affinity assays, and agonistic-function assays. The consistency between our computational design and wet-experimental measurements has led to our discovery of higher-affinity agonists of 5-HT1AR, with ～50-fold increase in receptor-binding affinity and ～25-fold improvements in agonistic function. In addition, our newly designed 5-HT1AR agonists showed very high selectivity of 5-HT1AR over subtype 5-HT2AR and also over three subtypes of dopamine receptors (D1, D2, and D3). (Graph Presented).
Lian, Peng,Li, Linlang,Geng, Chuanrong,Zhen, Xuechu,Fu, Wei
p. 1616 - 1627
(2015/09/01)

Ligand-free copper(i) oxide nanoparticle-catalysed amination of aryl halides in ionic liquids
In the following, we present a simple and feasible methodology for a C-N coupling reaction using nanoscale Cu2O catalysts incorporated in n-Bu4POAc ionic liquid media. It is shown that a wide range of amines and aryl halides can be coupled selectively in high yields, without the use of ligands or additives (bases) and without precautions against water or air. All catalyses can be carried out with a nanoparticle catalyst loading as low as 5 mol%, based on the used precursor.
Kessler, Michael T.,Robke, Silas,Sahler, Sebastian,Prechtl, Martin H. G.
p. 102 - 108
(2014/01/06)

Design of a bifunctional Ir-Zr based metal-organic framework heterogeneous catalyst for the N-alkylation of amines with alcohols
The direct N-alkylation of amines with alcohols was performed with an Ir-Zr-based metal-organic framework multifunctional heterogeneous catalyst. This system is efficient and environmentally benign for the synthesis of various organic amines in air in the absence of a base. The catalyst was recovered and reused without significant loss of activity, and only water was produced as a byproduct. Better be direct than elusive: The direct N-alkylation of amines with alcohols is performed with an Ir-Zr-based metal-organic framework multifunctional heterogeneous catalyst. This system is efficient and environmentally benign for the synthesis of various organic amines in air in the absence of a base. The catalyst is recovered and reused without significant loss of activity, and only water is produced as a byproduct.
Rasero-Almansa,Corma,Iglesias,Sanchez
p. 1794 - 1800
(2014/06/24)

Catalytic methylation of C-H bonds using CO2 and H2
Formation of C-C bonds from CO2 is a much sought after reaction in organic synthesis. To date, other than C-H carboxylations using stoichiometric amounts of metals, base, or organometallic reagents, little is known about C-C bond formation. In fact, to the best of our knowledge no catalytic methylation of C-H bonds using CO2 and H2 has been reported. Described herein is the combination of CO2 and H2 for efficient methylation of carbon nucleophiles such as indoles, pyrroles, and electron-rich arenes. Comparison experiments which employ paraformaldehyde show similar reactivity for the CO2/H2 system. Capturing: Carbon dioxide in the presence of H2 is shown to be an efficient methylating reagent for carbon nucleophiles such as 2-substituted indoles, pyrroles, and electron-rich arenes. Experimental data support the formal capture of formaldehyde. acac=acetylacetonate, triphos=1,1,1-tris(diphenylphosphinomethyl)ethane.
Li, Yuehui,Yan, Tao,Junge, Kathrin,Beller, Matthias
supporting information
p. 10476 - 10480
(2016/02/18)