- Method for preparing tertiary amine organic compound from photocatalytically decomposing substituted formamide
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The invention discloses a method for preparing a tertiary amine compound from aldehyde and substituted formamide under the action of a photocatalyst. The method is characterized in that the reaction can be performed only by illumination under the conditions of no hydrogen and no reducing agent. The method is suitable for various aldehydes including aromatic aldehydes, fatty aldehydes and the like,has the characteristics of few byproducts and high product yield, does not need to use hydrogen in the reaction, avoids the use of noble metal hydrogenation catalysts, and has obvious technical and economic effects and application prospects.
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Paragraph 0046-0048
(2021/01/12)
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- Pd(II)-Mediated C?H Activation for Cysteine Bioconjugation
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Selective bioconjugation remains a significant challenge for the synthetic chemist due to the stringent reaction conditions required by biomolecules coupled with their high degree of functionality. The current trailblazer of transition-metal mediated bioconjugation chemistry involves the use of Pd(II) complexes prepared via an oxidative addition process. Herein, the preparation of Pd(II) complexes for cysteine bioconjugation via a facile C?H activation process is reported. These complexes show bioconjugation efficiency competitive with what is seen in the current literature, with a user-friendly synthesis, common Pd(II) sources, and a more cost-effective ligand. Furthermore, these complexes need not be isolated, and still achieve high conversion efficiency and selectivity of a model peptide. These complexes also demonstrate the ability to selectively arylate a single surface cysteine residue on a model protein substrate, further demonstrating their utility.
- Frost, Christopher G.,Kociok-K?hn, Gabriele,Lubben, Anneke T.,Reeksting, Shaun B.,Tilden, James A. R.
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supporting information
(2022/01/19)
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- Simplified preparation of a graphene-co-shelled Ni/NiO@C nano-catalyst and its application in theN-dimethylation synthesis of amines under mild conditions
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The development of Earth-abundant, reusable and non-toxic heterogeneous catalysts to be applied in the pharmaceutical industry for bio-active relevant compound synthesis remains an important goal of general chemical research.N-methylated compounds, as one of the most essential bioactive compounds, have been widely used in the fine and bulk chemical industries for the production of high-value chemicals. Herein, an environmentally friendly and simplified method for the preparation of graphene encapsulated Ni/NiO nanoalloy catalysts (Ni/NiO@C) was developed for the first time, for the highly selective synthesis ofN-methylated compounds using various functional amines and aldehydes under easy to handle, and industrially applicable conditions. A large number of primary and secondary amines (more than 70 examples) could be converted to the correspondingN,N-dimethylamines with the participation of different functional aldehydes, with an average yield of over 95%. A gram-scale synthesis also demonstrated a similar yield when compared with the benchmark test. In addition, it was further proved that the catalyst could easily be recycled because of its intrinsic magnetism and reused up to 10 times without losing its activity and selectivity. Also, for the first time, the tandem synthesis ofN,N-dimethylamine products in a one-pot process, using only a single earth-abundant metal catalyst, whose activity and selectivity were more than 99% and 94%, respectively, for all tested substrates, was developed. Overall, the advantages of this newly developed method include operational simplicity, high stability, easy recyclability, cost-effectiveness of the catalyst, and good functional group compatibility for the synthesis ofN-methylation products as well as the industrially applicable tandem synthesis process.
- Liu, Jianguo,Ma, Longlong,Song, Yanpei,Zhang, Mingyue,Zhuang, Xiuzheng
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supporting information
p. 4604 - 4617
(2021/06/30)
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- Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
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Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
- Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
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p. 2059 - 2067
(2021/09/02)
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- Dimethylamination of Primary Alcohols Using a Homogeneous Iridium Catalyst: A Synthetic Method for N, N-Dimethylamine Derivatives
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A new catalytic system for N,N-dimethylamination of primary alcohols using aqueous dimethylamine in the absence of additional organic solvents has been developed. The reaction proceeds via borrowing hydrogen processes, which are atom-efficient and environmentally benign. An iridium catalyst bearing an N-heterocyclic carbene (NHC) ligand exhibited high performance, without showing any deactivation under aqueous conditions. In addition, valuable N,N-dimethylamine derivatives, including biologically active and pharmaceutical molecules, were synthesized. The practical application of this methodology was demonstrated by a gram-scale reaction.
- Jeong, Jaeyoung,Fujita, Ken-Ichi
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p. 4053 - 4060
(2021/03/09)
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- Palladium-Catalyzed Reductive Aminocarbonylation of Benzylammonium Triflates with o-Nitrobenzaldehydes for the Synthesis of 3-Arylquinolin-2(1 H)-ones
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A palladium-catalyzed straightforward procedure for the synthesis of 3-arylquinolin-2(1H)-ones has been developed. The synthesis proceeds through a palladium-catalyzed reductive aminocarbonylation reaction of benzylic ammonium triflates with o-nitrobenzaldehydes, and a wide range of 3-arylquinolin-2(1H)-ones was obtained in moderate to good yields with very good functional group compatibility.
- Liu, Yongzhu,Qi, Xinxin,Wu, Xiao-Feng
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p. 13824 - 13832
(2021/10/12)
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- Facile synthesis of controllable graphene-co-shelled reusable Ni/NiO nanoparticles and their application in the synthesis of amines under mild conditions
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The primary objective of many researchers in chemical synthesis is the development of recyclable and easily accessible catalysts. These catalysts should preferably be made from Earth-abundant metals and have the ability to be utilised in the synthesis of pharmaceutically important compounds. Amines are classified as privileged compounds, and are used extensively in the fine and bulk chemical industries, as well as in pharmaceutical and materials research. In many laboratories and in industry, transition metal catalysed reductive amination of carbonyl compounds is performed using predominantly ammonia and H2. However, these reactions usually require precious metal-based catalysts or RANEY nickel, and require harsh reaction conditions and yield low selectivity for the desired products. Herein, we describe a simple and environmentally friendly method for the preparation of thin graphene spheres that encapsulate uniform Ni/NiO nanoalloy catalysts (Ni/NiO?C) using nickel citrate as the precursor. The resulting catalysts are stable and reusable and were successfully used for the synthesis of primary, secondary, tertiary, and N-methylamines (more than 62 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, and H2 under very mild industrially viable and scalable conditions (80 °C and 1 MPa H2 pressure, 4 h), offering cost-effective access to numerous functionalized, structurally diverse linear and branched benzylic, heterocyclic, and aliphatic amines including drugs and steroid derivatives. We have also demonstrated the scale-up of the heterogeneous amination protocol to gram-scale synthesis. Furthermore, the catalyst can be immobilized on a magnetic stirring bar and be conveniently recycled up to five times without any significant loss of catalytic activity and selectivity for the product.
- Cui, Zhibing,Liu, Jianguo,Liu, Qiying,Ma, Longlong,Singh, Thishana,Wang, Chenguang,Wang, Nan,Zhu, Yuting
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supporting information
p. 7387 - 7397
(2020/11/19)
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- Cu2O-catalyzed C–S coupling of quaternary ammonium salts and sodium alkane-/arene-sulfinates
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A new protocol for the synthesis of (enantioenriched) benzylic sulfones via the Cu2O-catalyzed C–S bond cross coupling of alkane-/arene-sulfinates and (enantioenriched) benzylic quaternary ammonium salts has been developed. The product benzylic sulfones were obtained in good to high yields (75–96%). Chiral arylmethyl sulfones with high enantiomeric excess (90–94% ee) were also synthesized in the presence of Cu2O and 1,1′-bis-(diphenylphosphino)ferrocene (dppf).
- Chen, Hongyi,Huang, Youming,Zeng, Qingle,Zheng, Wenting
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supporting information
(2020/08/28)
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- Method for preparing tertiary amine organic compounds by using substituted formamide
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The invention discloses a method for preparing tertiary amine organic compounds by using substituted formamide. According to the method, aldehyde is used as a reaction substrate, substituted formamideis used as a solvent, reducing agent and aminating agent, a metal oxide/hydroxide is added as a catalyst, and a small amount of water is added as an auxiliary agent; heating and stirring are carriedout so as to form corresponding tertiary amine compounds; and a reaction can be conducted only through heating without hydrogen and a reducing agent. The method of the invention is applicable to various aldehydes including aromatic aldehydes, fatty aldehydes, etc., and has the characteristics of few by-products and high product yield; and hydrogen is not used in the reaction, and the use of a noble metal hydrogenation catalyst is avoided, so the method has remarkable technical and economic effects and application prospects.
- -
-
Paragraph 0034; 0035
(2019/01/24)
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- Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides
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New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH-ZnI2 system delivers alcohols and NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines.
- Ong, Derek Yiren,Yen, Zhihao,Yoshii, Asami,Revillo Imbernon, Julia,Takita, Ryo,Chiba, Shunsuke
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supporting information
p. 4992 - 4997
(2019/03/13)
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- Reductive Coupling between C-N and C-O Electrophiles
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The cross-electrophile reaction is a promising strategy for C-C bond formation. Recent studies have focused mainly on reactions with organic halides. Here we report a coupling reaction between C-N and C-O electrophiles that demonstrates the possibility of constructing a C-C bond via C-N and C-O cleavage. Several reactions between benzyl/aryl ammonium salts and vinyl/aryl C-O electrophiles have been studied. Preliminary mechanistic studies revealed that the benzyl ammoniums were activated through a radical mechanism.
- He, Rong-De,Li, Chun-Ling,Pan, Qiu-Quan,Guo, Peng,Liu, Xue-Yuan,Shu, Xing-Zhong
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supporting information
p. 12481 - 12486
(2019/09/04)
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- Methyl-Selective α-Oxygenation of Tertiary Amines to Formamides by Employing Copper/Moderately Hindered Nitroxyl Radical (DMN-AZADO or 1-Me-AZADO)
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Methyl-selective α-oxygenation of tertiary amines is a highly attractive approach for synthesizing formamides while preserving the amine substrate skeletons. Therefore, the development of efficient catalysts that can advance regioselective α-oxygenation at the N-methyl positions using molecular oxygen (O2) as the terminal oxidant is an important subject. In this study, we successfully developed a highly regioselective and efficient aerobic methyl-selective α-oxygenation of tertiary amines by employing a Cu/nitroxyl radical catalyst system. The use of moderately hindered nitroxyl radicals, such as 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO) and 1-methyl-2-azaadamanane N-oxyl (1-Me-AZADO), was very important to promote the oxygenation effectively mainly because these N-oxyls have longer life-times than less hindered N-oxyls. Various types of tertiary N-methylamines were selectively converted to the corresponding formamides. A plausible reaction mechanism is also discussed on the basis of experimental evidence, together with DFT calculations. The high regioselectivity of this catalyst system stems from steric restriction of the amine-N-oxyl interactions.
- Nakai, Satoru,Yatabe, Takafumi,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-ya,Mizuno, Noritaka,Yamaguchi, Kazuya
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supporting information
p. 16651 - 16659
(2019/11/11)
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- Electrochemical Dehydrogenative Imidation of N-Methyl-Substituted Benzylamines with Phthalimides for the Direct Synthesis of Phthalimide-Protected gem-Diamines
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A general and green electrochemical dehydrogenative method for the imidation of N-methyl benzylamines with phthalimides with excellent regioselectivities is reported for the first time. This operationally simple method offers a valuable tool to obtain str
- Lian, Fei,Sun, Caocao,Xu, Kun,Zeng, Chengchu
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supporting information
p. 156 - 159
(2019/01/11)
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- Selective synthesis of mono- and di-methylated amines using methanol and sodium azide as C1 and N1 sources
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A Ru(ii) complex mediated synthesis of various N,N-dimethyl and N-monomethyl amines from organic azides using methanol as a methylating agent is reported. This methodology was successfully applied for a one-pot reaction of bromide derivatives and sodium azide in methanol. Notably, by controlling the reaction time several N-monomethylated and N,N-dimethylated amines were synthesized selectively. The practical applicability of this tandem process was revealed by preparative scale reactions with different organic azides and synthesis of an anti-vertigo drug betahistine. Several kinetic experiments and DFT studies were carried out to understand the mechanism of this transformation.
- Chakrabarti, Kaushik,Mishra, Anju,Panja, Dibyajyoti,Paul, Bhaskar,Kundu, Sabuj
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supporting information
p. 3339 - 3345
(2018/07/29)
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- Well-Defined Phosphine-Free Iron-Catalyzed N-Ethylation and N-Methylation of Amines with Ethanol and Methanol
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An iron(0) complex bearing a cyclopentadienone ligand catalyzed N-methylation and N-ethylation of aryl and aliphatic amines with methanol or ethanol in mild and basic conditions through a hydrogen autotransfer borrowing process is reported. A broad range of aromatic and aliphatic amines underwent mono- or dimethylation in high yields. DFT calculations suggest molecular hydrogen acts not only as a reducing agent but also as an additive to displace thermodynamic equilibria.
- Lator, Alexis,Gaillard, Sylvain,Poater, Albert,Renaud, Jean-Luc
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supporting information
p. 5985 - 5990
(2018/10/02)
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- Efficient and versatile catalytic systems for the n-methylation of primary amines with methanol catalyzed by n-heterocyclic carbene complexes of iridium
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Efficient and versatile catalytic systems were developed for the N-methylation of both aliphatic and aromatic primary amines using methanol as the methylating agent. Iridium complexes bearing an Nheterocyclic carbene (NHC) ligand exhibited high catalytic performance for this type of transformation. For aliphatic amines, selective N,N-dimethylation was achieved at low temperatures (50-90 °C). For aromatic amines, selective N-monomethylation and selective N,N-dimethylation were accomplished by simply changing the reaction conditions (presence or absence of a base with an appropriate catalyst). These findings can be used to develop methods for synthesizing useful amine compounds having N-methyl or N,N-dimethyl moieties.
- Toyooka, Genki,Tuji, Akiko,Fujita, Ken-Ichi
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p. 4617 - 4626
(2019/02/01)
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- The sustainable heterogeneous catalytic reductive amination of lignin models to produce aromatic tertiary amines
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A novel heterogeneous catalytic process for efficient reductive amination is developed in the presence of heterogeneous zirconium-based catalysts, in which N,N-dimethylformamide is used as the solvent, low-molecular-weight amine source and reductant. Aromatic tertiary amines have been produced from lignin-derived aromatic aldehydes via the mild Leuckart reaction with ZrO2 or ZrO(OH)2 as catalysts, for instance, a 95.8% yield of N,N-dimethyl-1-(3,4,5-trimethoxyphenyl)methanamine in a 100% selectivity is obtained from the reductive amination of 3,4,5-trimethoxybenzaldehyde under mild conditions.
- Zhang, Haigang,Tong, Xinli,Liu, Zonghui,Wan, Jun,Yu, Linhao,Zhang, Zhenya
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p. 5396 - 5400
(2018/11/20)
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- Visible-Light-Mediated α-Oxygenation of 3-(N,N-Dimethylaminomethyl)-Indoles to Aldehydes
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The visible-light-mediated oxygenation of 3-N,N-(dimethylaminomethyl)-indoles bearing various substituents afforded a series of 3-carbaindole derivatives. Herein we describe the reaction scope, a plausible mechanism and a practical application of this transformation in the formal synthesis of (–)-vincorine is described as well.
- Stanek, Filip,Paw?owski, Robert,Mlynarski, Jacek,Stodulski, Maciej
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supporting information
p. 6624 - 6628
(2018/10/20)
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- Remarkably high catalyst efficiency of a disilaruthenacyclic complex for hydrosilane reduction of carbonyl compounds
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A disilaruthenacyclic complex (1) showed extremely high catalytic activity for hydrosilane reduction of aldehydes and ketones to silyl ethers and secondary and tertiary amides to the corresponding amines. An σ-CAM mechanism was proposed to explain the activity.
- Tahara, Atsushi,Sunada, Yusuke,Takeshita, Takashi,Inoue, Ryoko,Nagashima, Hideo
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supporting information
p. 11192 - 11195
(2018/10/24)
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- Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction
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A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.
- Li, Huaifeng,Gon?alves, Théo P.,Zhao, Qianyi,Gong, Dirong,Lai, Zhiping,Wang, Zhixiang,Zheng, Junrong,Huang, Kuo-Wei
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supporting information
p. 11395 - 11398
(2018/10/20)
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- Reduction and Reductive Deuteration of Tertiary Amides Mediated by Sodium Dispersions with Distinct Proton Donor-Dependent Chemoselectivity
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A practical and scalable single electron transfer reduction mediated by sodium dispersions has been developed for the reduction and reductive deuteration of tertiary amides. The chemoselectivity of this method highly depends on the nature of the proton donor. The challenging reduction via C-N bond cleavage has been achieved using Na/EtOH, affording alcohol products, while the use of Na/NaOH/H2O leads to the formation of amines via selective C-O scission. Sodium dispersions with high specific surface areas are crucial to obtain high yields and good chemoselectivity. This new method tolerates a range of tertiary amides. Moreover, the corresponding reductive deuterations mediated by Na/EtOD-d1 and Na/NaOH/D2O afford useful α,α-dideuterio alcohols and α,α-dideuterio amines with an excellent deuterium content.
- Zhang, Bin,Li, Hengzhao,Ding, Yuxuan,Yan, Yuhao,An, Jie
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p. 6006 - 6014
(2018/05/24)
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- Direct Synthesis of N,N-Dimethylated and β-Methyl N,N-Dimethylated amines from nitriles using methanol: Experimental and computational studies
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Direct and selective synthesis of N,N-dimethylated amines from nitriles using methanol as C1 building blocks is reported using an air- and moisture-stable ruthenium complex. Following this process, various aromatic as well as aliphatic nitriles were converted to the corresponding N-methylated amines. Interestingly, tandem C-methylation as well as N-methylation was achieved by introducing multiple methyl groups. The practical aspect of this process was revealed by preparative-scale reactions with different nitriles and the synthesis of anti-allergic drug "avil". Several kinetic experiments and detailed DFT calculations were carried out to understand the mechanism of this process.
- Paul, Bhaskar,Shee, Sujan,Panja, Dibyajyoti,Chakrabarti, Kaushik,Kundu, Sabuj
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p. 2890 - 2896
(2018/04/14)
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- Lewis Acid-Catalyzed Reductive Amination of Aldehydes and Ketones with N,N-Dimethylformamide as Dimethylamino Source, Reductant and Solvent
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A practical zinc acetate dihydrate-catalyzed reductive amination of various carbonyl compounds with N,N-dimethylformamide (DMF) as dimethylamino (Me2N) source, reductant and solvent has been developed. This reaction shows broad substrate scope,
- Yang, Luo,Lin, Jie,Kang, Lei,Zhou, Wang,Ma, Da-You
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supporting information
p. 485 - 490
(2018/01/15)
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- Efficient Cobalt-Catalyzed Methylation of Amines Using Methanol
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The methylation of amines using methanol is a promising route to synthesize N-methylamines, and the development of cheap and efficient catalytic system for this reaction is of great significance. Herein, we reported a cobalt (Co)-based catalytic system, which was in situ formed from commercially available Co precursor and a tetradentate phosphine ligand P(CH2CH2PPh2)3 combined with K3PO4. This catalystic system was very effective for the selective production of dimethylated products from aliphatic amines and monomethylated ones from aromatic amines. The reaction mechanism was further investigated by control and isotope labelling experiments. (Figure presented.).
- Liu, Zhenghui,Yang, Zhenzhen,Yu, Xiaoxiao,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
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supporting information
p. 4278 - 4283
(2017/10/23)
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- Ionic liquid/H2O-mediated synthesis of mesoporous organic polymers and their application in methylation of amines
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Mesoporous Tr?ger's base-functionalized polymers (Meso-TBPs) were prepared using a sulfonic acid group functionalized ionic liquid/H2O system, with surface areas up to 431 m2 g-1 and pore sizes of 3-15 nm. Ir(ii) coordinated Meso-TBPs exhibited extraordinary catalytic performance in the N-methylation of amines using methanol.
- Yu, Xiaoxiao,Yang, Zhenzhen,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liiu, Zhenghui,Ji, Guipeng,Liu, Zhimin
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supporting information
p. 5962 - 5965
(2017/07/10)
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- MONONUCLEAR RUTHENIUM COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbon
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- MONONUCLEAR IRON COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Provided is a mononuclear iron complex that comprises an iron-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R1-R6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R1-R3 and one of R4-R6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
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- Chemoselective Reduction of Tertiary Amides to Amines Catalyzed by Triphenylborane
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Triphenylborane (BPh3) was found to catalyze the reduction of tertiary amides with hydrosilanes to give amines under mild condition with high chemoselectivity in the presence of ketones, esters, and imines. N,N-Dimethylacrylamide was reduced to provide the α-silyl amide. Preliminary studies indicate that the hydrosilylation catalyzed by BPh3may be mechanistically different from that catalyzed by the more electrophilic B(C6F5)3.
- Mukherjee, Debabrata,Shirase, Satoru,Mashima, Kazushi,Okuda, Jun
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supporting information
p. 13326 - 13329
(2016/10/30)
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- Reductive N-methylation of amines with calcium hydride and Pd/C catalyst
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The methylation of amines by paraformaldehyde in the presence of calcium hydride as a source of hydrogen and palladium on charcoal as catalyst was studied. Depending on the quantity of paraformaldehyde, monomethylated and dimethylated amines were selectively and efficiently prepared in one pot with good yields.
- Guyon, Carole,Duclos, Marie-Christine,Métay, Estelle,Lemaire, Marc
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p. 3002 - 3005
(2016/07/06)
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- Light-promoted N,N-dimethylation of amine and nitro compound with methanol catalyzed by Pd/TiO2 at room temperature
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A series of TiO2 supported nano-Pd catalysts (Pd/TiO2) were prepared and used for the N,N-dimethylation of different amines and nitro compounds with methanol under UV irradiation at room temperature. A wide range of N,N-dimethyl amines were one-pot synthesized with up to 98% by applying aliphatic secondary amines, aromatic primary amines, aliphatic primary amines and aromatic nitro compounds as starting materials. It is noteworthy that up to 90% yield of 4-chloro-N,N-dimethylaniline was obtained by adjusting the Pd loadings on the TiO2 and the dehalogenation reaction was inhibited. Finally, a reaction mechanism is discussed, involving PhN = CH2 and PhNHCH3 as reaction intermediates.
- Zhang, Lina,Zhang, Yan,Deng, Youquan,Shi, Feng
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p. 14514 - 14521
(2015/03/05)
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- MONONUCLEAR IRON COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Provided is a mononuclear iron complex that comprises an iron-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R 1 -R 6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R 1 -R 3 and one of R 4 -R 6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
- -
-
Paragraph 0295-0297
(2016/12/01)
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- MONONUCLEAR RUTHENIUM COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
-
Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R 1 -R 6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R 1 -R 3 and one of R 4 -R 6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO and phosphine. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
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Paragraph 0239-0241
(2017/01/02)
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- Dual antitumor and antiangiogenic activity of organoplatinum(II) complexes
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A library of over 20 cycloplatinated compounds of the type [Pt(dmba-R)LCl] (dmba-R = C,N-dimethylbenzylamine-like ligand; R being MeO, Me, H, Br, F, CF3, and NO2 substituents in the R5 or R4 position of the phenyl ring; L = DMSO and P(C6H4CF3-p)3) has been prepared. All compounds are active in both human ovarian carcinoma A2780 cells and cisplatin-resistant A2780cisR cells, with most of the DMSO platinum complexes exhibiting IC50 values in the submicromolar range in the A2780 cell line. Interestingly, DMSO platinum complexes show low cytotoxicity in the nontumorigenic kidney cell line BGM and therefore high selectivity factors SF. In addition, some of the DMSO platinum complexes effectively inhibit angiogenesis in the human umbilical vein endothelial cell line EA.hy926. These are the first platinum(II) complexes reported to inhibit angiogenesis at a close concentration to their IC50 in A2780 cells, turning them into dual cytotoxic and antiangiogenic compounds.
- Zamora, Ana,Pérez, Sergio A.,Rodríguez, Venancio,Janiak, Christoph,Yellol, Gorakh S.,Ruiz, José
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p. 1320 - 1336
(2015/03/04)
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- PROCESS FOR PRODUCING N-METHYL OR N,N-DIMETYL AMINES
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A process for producing N-methyl or N,N-dimethyl amines, which comprises using amine compound, nitro-containing compound or nitrile compound as a starting material, carbon dioxide as a methylating agent and hydrogen gas as a reducing agent, and allowing them to react in a sealed reactor for 6 to 48 h in a reaction medium at a reaction temperature of 80 to 180 ° C. in the presence of a composite catalyst, so as to provide N-methyl or N,N-dimethyl amines. The process of the present invention is simple and under relative mild reaction conditions. By means of the process of the invention, the target products can be prepared at low cost with a high yield. The catalysts used have a high catalytic activity and can be separated from the reaction system simply and reused. Furthermore, the whole process of the present invention is environmental-friendly and facilitates the cycling use of carbon dioxide.
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Paragraph 0059
(2015/02/18)
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- Direct reductive alkylation of amine hydrochlorides with aldehyde bisulfite adducts
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A mild procedure for the direct reaction of aromatic and aliphatic aldehyde bisulfite adducts with primary and secondary amine hydrochlorides in the presence of sodium cyanoborohydride in methanol is reported.
- Barniol-Xicota, Marta,Turcu, Andreea L.,Codony, Sandra,Escolano, Carmen,Vázquez, Santiago
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p. 2548 - 2550
(2014/05/06)
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- Methylation of amines, nitrobenzenes and aromatic nitriles with carbon dioxide and molecular hydrogen
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CO2/H2 was successfully employed in alkylation reactions by performing CO2 reduction and amine N-methylation in one-pot. In the presence of a simple CuAlOx catalyst, N-methyl or N,N-dimethyl amines with different structures can be selectively synthesized with up to 96% yields by applying amine, nitrobenzene and nitrile as starting materials.
- Cui, Xinjiang,Dai, Xingchao,Zhang, Yan,Deng, Youquan,Shi, Feng
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p. 649 - 655
(2014/01/17)
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- METHOD FOR PRODUCING N-SUBSTITUTED AMINE COMPOUNDS THROUGH CATALYZED ALKYLATION
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The invention relates to a method for producing a N-substituted amine compound by catalyzed alkylation. The method uses amine and alcohol or two kinds of amines as the reaction materials, employs composite metal oxides catalyst at a reaction temperature of 80-180° C. to catalyze the reaction for 6-36 hours, so as to produce the N-substituted amine compound. The reaction condition of the method of the invention is relatively moderate, using a catalyst made of cheap non-noble metals, which is non-caustic and easy to be separated and reused. The reaction does not need any medium and has relatively high conversion rate and selectivity.
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Paragraph 0044
(2014/02/16)
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- Catalyst design for iron-promoted reductions: An iron disilyl-dicarbonyl complex bearing weakly coordinating η2-(H-Si) moieties
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Iron disilyl dicarbonyl complex 1, in which two H-Si moieties of the 1,2-bis(dimethylsilyl)benzene ligand were coordinated to the iron center in an η2-(H-Si) fashion, was synthesized by the reaction of (η4-C6H8)Fe(CO)3 with 2 equiv. of 1,2-bis(dimethylsilyl)benzene under photo-irradiation. Complex 1 demonstrated high catalytic activity toward the hydrogenation of alkenes, the hydrosilylation of alkenes and the reduction of carbonyl compounds.
- Sunada, Yusuke,Tsutsumi, Hironori,Shigeta, Keisuke,Yoshida, Ryota,Hashimoto, Toru,Nagashima, Hideo
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p. 16687 - 16692
(2013/12/04)
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- Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia
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The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation. Copyright
- Cui, Xinjiang,Dai, Xingchao,Deng, Youquan,Shi, Feng
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supporting information
p. 3665 - 3675
(2013/03/29)
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- Cu(II)-promoted palladium-catalyzed C-H ortho-arylation of N, N-dimethylbenzylamines
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A novel protocol for palladium-catalyzed arylation of the C(sp 2)-H bond directed by a N,N-dimethylaminomethyl group in the presence of AgOAc and Cu(OAc)2·H2O is described. Various aryl iodides proved to be efficient coupl
- Feng, Ruokun,Yao, Jinzhong,Liang, Zunjun,Liu, Zhanxiang,Zhang, Yuhong
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p. 3688 - 3696
(2013/06/04)
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- New catalyst systems for iron-catalyzed hydrosilane reduction of carboxamides
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A heptanuclear iron carbonyl cluster, [Fe3(CO) 11(μ-H)]2Fe(DMF)4 (4), is found to be a highly efficient catalyst for the reduction of various carboxamides by 1,2-bis(dimethylsilyl)benzene (BDSB), which makes possible reducing the amount of the catalyst, shortening the reaction time, and lowering the reaction temperatures.
- Tsutsumi, Hironori,Sunada, Yusuke,Nagashima, Hideo
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supporting information; experimental part
p. 6581 - 6583
(2011/07/08)
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- Highly efficient gold nanoparticle catalyzed deoxygenation of amides, sulfoxides, and pyridine N-oxides
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Selective deoxygenation is one of the most important reactions in the areas of total synthesis, biological chemistry, and transformation of renewable biomass resources.To date, many useful methods for the selective deoxygenation of oxygen-containing organic molecules, such as amides, nitro compounds, epoxides, sulfoxides, and those with Noxide groups, have been developed. However, these methods often include stoichiometric reactions. Some successful catalysts have been reported,but most of them are homogeneous systems and still suffer from low activities and selectivities, harsh reaction conditions, and tedious workup procedures. Therefore, further development of highly efficient heterogeneous catalysts for selective deoxygenations is highly desired.
- Mikami, Yusuke,Noujima, Akifumi,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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experimental part
p. 1768 - 1772
(2011/03/21)
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- Borrowing hydrogen in water and ionic liquids: Iridium-catalyzed alkylation of amines with alcohols
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The use of [Cp*IrI2]2 as an efficient catalyst for the alkylation of amines by alcohols in either water or ionic liquid is described. Primary amines are converted into secondary amines, and secondary amines into tertiary amines in the absence of base, and the chemistry has been applied to the synthesis of the analgesic fentanyl. The conversion of primary amines into N-heterocycles by the reaction with diols is also described, along with the N-alkylation of sulfonamides.
- Saidi, Ourida,Blacker, A. John,Lamb, Gareth W.,Marsden, Stephen P.,Taylor, James E.,Williams, Jonathan M. J.
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supporting information; experimental part
p. 1046 - 1049
(2011/03/20)
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- LiCl-Promoted Pd(ii)-catalyzed ortho carbonylation of N,N- dimethylbenzylamines
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Palladium-catalyzed highly regioselective carbonylation of substituted N,N-dimethylbenzylamines with the assistance of LiCl was developed. The ortho-functionalized N,N-dimethylbenzylamine was further transformed into ortho-methyl benzoate under mild conditions. These two transformations could be combined into one pot to produce the desired product in moderate yield. Applications of this methodology to synthesize the fragments of variolaric acid were also studied.
- Li, Hu,Cai, Gui-Xin,Shi, Zhang-Jie
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supporting information; experimental part
p. 10442 - 10446
(2011/01/08)
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- Practical access to amines by platinum-catalyzed reduction of carboxamides with hydrosilanes: Synergy of dual Si-H groups leads to high efficiency and selectivity
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The synergetic effect of two Si-H groups leads to efficient reduction of carboxamides to amines by platinum catalysts under mild conditions. The rate of the reaction is dependent on the distance of two Si-H groups; 1,1,3,3-tetramethyldisiloxane (TMDS) and 1,2-bis(dimethylsilyl)benzene are found to be an effective reducing reagent. The reduction of amides having other reducible functional groups such as NO2, CO2R, CN, CdC, Cl, and Br moieties proceeds with these groups remaining intact, providing a reliable method for the access to functionalized amine derivatives. The platinum-catalyzed reduction of amides with polymethylhydrosiloxane (PMHS) also proceeds under mild conditions. The reaction is accompanied by automatic removal of both platinum and silicon wastes as insoluble silicone resin, and the product is obtained by simple extraction. A mechanism involving double oxidative addition of TMDS to a platinum center is discussed.
- Hanada, Shiori,Tsutsumi, Emi,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 15032 - 15040
(2010/01/29)
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- Hydrosilane reduction of tertiary carboxamides by iron carbonyl catalysts
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Fox in the carboxamide: Reduction of tertiary carboxamides to their corresponding amines is catalyzed by [Fe(CO)5] or [Fe 3(CO)12], using 1,1,3,3tetramethyldlsiloxane (TMDS) as the reducing agent. The reaction proceeds under either thermal or photochemical conditions. Unlike the hydrosilane reduction of amides using platinum or ruthenlum catalysts, TMDS preferentially reduces a nitro group, even in the presence of competing amides.
- Sunada, Yusuke,Kawakami, Hiroko,Imaoka, Tsuyoshi,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 9511 - 9514
(2010/03/24)
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- Indirect ortho functionalization of substituted toluenes through ortho olefination of N,N-dimethylbenzylamines tuned by the acidity of reaction conditions
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Highly regioselective olefination of substituted N,N-dimethylbenzylamines was developed by tuning the acidity of reaction conditions based on analysis of their features. The ortho-functionalized N,N-dimethylbenzylamines were further transformed into 3-(2′
- Cai, Guixin,Fu, Ye,Li, Yizhou,Wan, Xiaobing,Shi, Zhangjie
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p. 7666 - 7673
(2008/02/09)
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- Asymmetric Sommelet-Hauser rearrangement of N-benzylic ammonium salts
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(Chemical Equation Presented) [2,3] over [1,2]: The asymmetric Sommelet-Hauser rearrangement of an ammonium salt derived from N-benzylic proline-derived or N-benzylic glycine (-)-8-phenylmenthol ester is shown to proceed with remarkably high levels of stereoselectivity. The method provides unique and efficient access to optically active α-aryl amino acid derivatives.
- Tayama, Eiji,Kimura, Hiroshi
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p. 8869 - 8871
(2008/09/19)
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- Dual Si-H effects in platinum-catalyzed silane reduction of carboxamides leading to a practical synthetic process of tertiary-amines involving self-encapsulation of the catalyst species into the insoluble silicone resin formed
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Combination of commercially available platinum catalysts with siloxanes containing more than two Si-H groups is found to be an efficient catalyst system for the reduction of carboxamides to amines. In particular, facile removal of silicon and platinum residues from the product can be achieved by the use of polymethylhydrosiloxanes as reducing reagents.
- Hanada, Shiori,Motoyama, Yukihiro,Nagashima, Hideo
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p. 6173 - 6177
(2007/10/03)
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- Selective N-methylation of primary aliphatic amines with dimethyl carbonate in the presence of alkali cation exchanged Y-faujasites
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The N-methylation of aliphatic amines [XC6H4(CH 2)nNH2; n=1, X=H (1a), o-MeO (1b), p-MeO (1c); n=2, X=H (2a), o-MeO (2b); 1d: PhCH(Me)NH2] with dimethyl carbonate (DMC) is efficiently catalysed by NaY faujasite: on condition that CO 2 (a co-product of the reaction) is carefully removed, N-methyl- and N,N-dimethyl-amines (RNHMe and RNMe2) are obtained in good overall yields (70-90%). Otherwise, in the presence of CO2, carbamates (RNHCO2Me) form competitively to a large extent. The reaction probably proceeds through a BAl2 displacement of the amine on DMC.
- Selva, Maurizio,Tundo, Pietro
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p. 8139 - 8142
(2007/10/03)
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