- Efficient Co-Catalyzed Double Hydroboration of Nitriles: Application to One-Pot Conversion of Nitriles to Aldimines
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The commercially available and bench-stable Co(acac)2/dpephos system is employed as a precatalyst for selective and efficient room temperature hydroboration of organic nitriles with HBPin to produce a series of N,N-diborylamines [RN(BPin)2], which react in situ with aldehydes to give aldimines. Formation of aldimines from N,N-diborylamines does not require a dehydrating agent, is applicable to a wide range of N,N-diborylamine and aldehyde substrates and is highly chemoselective, being unaffected by various common functional groups, such as alkenes, alkynes, secondary amines, ketones, esters, amides, carboxylic acids, pyridines, nitriles, and nitro compounds. The overall transformation represents a synthetically valuable approach to aldimines from nitriles and can be performed in a sequential one-pot manner, tolerating ester, lactone, carboxamide and unactivated alkene functionalities.
- Gudun, Kristina A.,Slamova, Ainur,Hayrapetyan, Davit,Khalimon, Andrey Y.
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p. 4963 - 4968
(2020/04/17)
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- Crystal structure, hirshfeld surface analysis and energy framework study of the nitrone n-benzylidene-n-butylamino-4-β-pyridyl-n-oxide
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The title compound, C16H16N2O, a potential antiparasitic agent, crystallizes in the orthorhombic Pca21 space group with unit cell parameters a= 9.912(1) ?, b= 9.035(1) ?, c= 15.681(2) ?. The crystalline structure is stabilized by weak C-H···O and C-H···Cg(π) interactions among neighboring molecules producing an efficient packing with 66.0% of occupied space. The C-H···O hydrogen bond keeps the molecules linked into supramolecular chains propagating along the a axis direction with a graph-set notation C(4), which are reinforced by C-H···Cg(π) interactions. Hirshfeld surface analysis of the intermolecular contacts reveal that the most important contributions for the crystal packing are from H··H (55.2%) and H··C/C··H (27.1%) interactions. Energy framework calculations suggest that the contacts formed between molecules are slightly dispersive in nature.
- Bahsas, Ali,Brito, Iván,Cárdenas, Alejandro,Chacón, Cecilia,Cisterna, Jonathan,Delgado, Gerzon E.,Koustnetzov, Vladimir V.,Mora, Asiloé J.
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p. 4865 - 4869
(2020/11/16)
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- Selective aerobic oxidation of halides and amines with an inorganic-ligand supported zinc catalyst
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A practical, efficient and environmentally benign catalytic protocol for the oxidative cross-coupling reaction of halides with amines, oxidative self-coupling of amines and oxidation of halides was developed with inorganic-ligand supported ZnPOM (NH4)4[ZnMo6O18(OH)6] using molecular oxygen. This method mainly utilizes an inorganic polymolybdate ligand to support the Zn2+ ion, avoiding the use of complicated organic ligands.
- Wang, Jingjing,Zhai, Yongyan,Wang, Ying,Yu, Han,Zhao, Wenshu,Wei, Yongge
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p. 13323 - 13327
(2018/10/15)
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- Visible-Light-Driven Photocatalytic Oxidation of Organic Chlorides Using Air and an Inorganic-Ligand Supported Nickel-Catalyst Without Photosensitizers
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Engineering photoredox-triggered chemical transformation via visible light has been an emerging area in organic synthesis. However, most of the well-established photocatalysts are based upon either transition metal complexes involved with noble metals and organic ligands or photosensitive organic dyes, the development of pure inorganic molecular photocatalysts that could provide better stability and durability is greatly retarded. Herein we discover that the Anderson polyoxometalate (POM) Na4[NiMo6O18(OH)6] (1), which consists of pure inorganic framework built from a central NiII core supported by six MoVIO6 inorganic scaffold/ligands, can be used as a powerful photocatalyst. Upon irradiation with visible light (>400 nm), the compound can catalyze, in high efficiency, a wide range of reactions, including the oxidative cross-coupling reaction of chlorides with amines, as well as oxidation of chlorides using molecular oxygen, affording various imines, aldehydes, and ketones, respectively in high selectivity and good yields. Owing to the robust inorganic framework, this catalyst exhibits excellent stability during the catalysis and reusability with little loss of the catalytic activity, thus providing an alternative without use of complicated organic ligands and expensive noble metal-based photosensitizers.
- Yu, Han,Wang, Jingjing,Zhai, Yongyan,Zhang, Mengqi,Ru, Shi,Han, Sheng,Wei, Yongge
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p. 4274 - 4279
(2018/09/10)
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- Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines
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Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH4)n[MMo6O18(OH)6] (M=Cu2+; Fe3+; Co3+; Ni2+; Zn2+, n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six MoVI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis.
- Yu, Han,Zhai, Yongyan,Dai, Guoyong,Ru, Shi,Han, Sheng,Wei, Yongge
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supporting information
p. 13883 - 13887
(2017/10/13)
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- Mechanochemical lignin-mediated strecker reaction
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A mechanochemical Strecker reaction involving a wide range of aldehydes (aromatic, heteroaromatic and aliphatic), amines, and KCN afforded a library of α-aminonitriles upon mechanical activation. This multicomponent process was efficiently activated by li
- Dabral, Saumya,Turberg, Mathias,Wanninger, Andrea,Bolm, Carsten,Hernández, José G.
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- Method for synthesizing imine through cross-coupling of hydroxylation phenanthroline copper complex/O2 catalytic oxidation alcohol and amine
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The invention discloses a method for synthesizing imine through cross-coupling of hydroxylation phenanthroline copper complex/O2 catalytic oxidation alcohol and amine. According to the method, an economical and cheap hydroxylation phenanthroline copper complex is selected as a catalyst, green O2 is selected as an oxidizing agent, cross-coupling of alcohol and amine is realized under the condition of normal temperature, alkali and an expensive free radical of nitroxide is prevented from being used, and a series of imine compounds are successfully prepared. The method provided by the invention is high in reaction selectivity and relatively wide in a substrate application range, and has a great industrial application potential.
- -
-
Paragraph 0017; 0030; 0031
(2017/12/02)
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- Facile synthesis of litchi shaped cuprous oxide and its application in the aerobic oxidative synthesis of imines
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In the present work, uniform litchi shaped cuprous oxide (Cu2O) nanoaggregates were synthesized via a facile method by employing copper(ii) chloride, sodium hydroxide, ethylene glycol and ascorbic acid in the absence of surfactants at room temperature. With further increase of the reaction temperature, broken hollow copper nanoaggregates were obtained. The structure of a Cu2O nanoaggregate was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Transmission Electron Microscopy (TEM), Brunauer-Emmett-Teller (BET) analysis and High Resolution Transmission Electron Microscopy (HRTEM). The as-obtained Cu2O nanoaggregates showed efficient catalytic activities in the aerobic oxidative synthesis of imines.
- Bai, Lei,Dang, Zheng
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p. 10341 - 10345
(2015/02/05)
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- Palladium-catalyzed [4 + 2] cycloaddition of aldimines and 1,4-dipolar equivalents via amphiphilic allylation
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The combination of Pd catalyst and diethylzinc with triethylborane promotes the amphiphilic allylation of aldimines with 2,3-bismethylenebutane-1,4-diol derivatives to serve as bis-allylic zwitterion species to form 3,4-bismethylenepiperidines via a formal [4 + 2] cycloaddition reaction. 3,4-Bismethylenepiperidine rings are applicable for the synthesis of isoquinoline derivatives via the Diels-Alder reaction followed by an oxidation reaction with DDQ.
- Hirata, Goki,Yamada, Naoshi,Sanada, Shohei,Onodera, Gen,Kimura, Masanari
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supporting information
p. 600 - 603
(2015/03/04)
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- Flow synthesis of organic azides and the multistep synthesis of imines and amines using a new monolithic triphenylphosphine reagent
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Here we describe general flow processes for the synthesis of alkyl and aryl azides, and the development of a new monolithic triphenylphosphine reagent, which provides a convenient format for the use of this versatile reagent in flow. The utility of these new tools was demonstrated by their application to a flow Staudinger aza-Wittig reaction sequence. Finally, a multistep aza-Wittig, reduction and purification flow process was designed, allowing access to amine products in an automated fashion.
- Smith, Catherine J.,Smith, Christopher D.,Nikbin, Nikzad,Ley, Steven V.,Baxendale, Ian R.
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supporting information; experimental part
p. 1927 - 1937
(2011/04/21)
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- Application of bis(trimethylsilyl) phosphonite in the efficient preparation of new heterocyclic -aminomethyl- H -phosphinic acids
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A simple, reproducible, and efficient preparation of new heterocyclic -aminomethyl-H-phosphinic acids is reported. The synthetic protocol is based on the application of bis(trimethylsilyl) phosphonite, as an efficient phosphorous nucleophile, in the reaction with the corresponding heterocyclic imines. Subsequent methanolysis of the addition intermediates leads to the expected heterocyclic -aminomethyl-H-phosphinic acids in fair to good yields. Additionally, acidic hydrolysis of benzhydrylamino derivatives allows the efficient preparation of free -aminomethyl-H-phosphinic acids in good yields and high purity after simple crystallization. Georg Thieme Verlag Stuttgart New York.
- Olszewski, Tomasz K.,Boduszek, Bogdan
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experimental part
p. 437 - 442
(2011/04/22)
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- Preparation of dialkyl 1-(Alkylamino)alkylphosphonates, alkyl [1-(Alkylamino)alkyl]phenylphosphinates and [1-(Alkylamino)alkyl] diphenylphosphine oxides via in situ generated iminium ions
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The reaction of trialkyl phosphites, dialkyl phenylphosphonites or alkyl diphenylphosphinites with N-alkylalkanimines in the presence of hydrogen chloride gives dialkyl 1-(alkylamino)alkylphosphonates, alkyl amino)alkyl]phenylphosphinates or [1-(alkylamino)alkyl]diphenylphosphine oxides respectively, via Arbusov-like reaction of iminium salts generated in situ from N-alkylalkanimines. This reaction is an alternative and competitive to known method of preparation based on the addition of H-P compounds to N-alkylalkanimines, because it gives higher yields, no heating is necessary, and the isolation of products is easy. Georg Thieme Verlag Stuttgart · New York.
- Goldeman, Waldemar,Soroka, Miroslaw
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experimental part
p. 2437 - 2445
(2010/09/04)
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- Staudinger/aza-Wittig reactions utilizing a novel linear polymer-supported triphenylphosphine as a modified liquid-phase reagent
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A new triphenylphosphine reagent linked to a linear maleimide-styrene copolymer is synthesized and is found to be effective for the formation of a variety of imines via the Staudinger/aza-Wittig reaction. This linear polymer-supported triphenylphosphine h
- Mahdavi, Hossein,Amani, Javad
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experimental part
p. 5923 - 5926
(2010/01/11)
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- Aminophosphinic acids in a pyridine series, Part 2: Synthesis of 2-, 3-, and 4-pyridyl derivatives of 1-(Benzylamino)-methyl-H-phosphinic Acids
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New 2-pyridyl, 3-pyridyl, and 4-pyridyl derivatives of 1-[N-(benzyl)amino]- methyl-H-phosphinic acid were prepared by the addition of bis(trimethylsilyl) phosphonite to the corresponding imines and subsequent methanolysis of the addition products. Treatment of the 2-pyridyl- and 1-(4-pyridyl)-1-(benzylamino) -methyl-H-phosphinic acids with aqueous mineral acids leads to cleavage and formation of the corresponding secondary amines and phosphorous acid (H3PO3).
- Goldeman, Waldemar,Boduszek, Bogdan
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experimental part
p. 1413 - 1425
(2010/03/24)
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- Aminophosphinic acids in a pyridine series: Cleavage of pyridine-2- and pyridine-4-methyl(amino)phosphinic acids in acidic solutions
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The synthesis of a series of new pyridine aminomethylphosphinic acids is described. These compounds were obtained in the reaction of the corresponding pyridine aldehydes with primary amines and with ethyl phenylphosphinate, or methylphosphinate, in the presence of bromotrimethylsilane. In aqueous, strong acid solutions, pyridine aminophosphinic acids were split, forming the phenyl-, or methylphosphonic, acid and the corresponding secondary pyridyl-alkylamines. The kinetics of some observed cleavages were measured, and a mechanism of the cleavage has been proposed. Copyright Taylor & Francis Group, LLC.
- Boduszek, Bogdan,Olszewski, Tomasz,Goldeman, Waldemar,Konieczna, Magdalena
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p. 787 - 795
(2007/10/03)
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- A new 'one-pot' synthesis of 2-substituted 3-nitro pyrrolidines through a multicomponent domino reaction
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An efficient 'one-pot' synthesis of the title compounds based on a multicomponent domino reaction between imines and 3-nitro-1-propanol methanesulfonate has been developed.
- Baricordi, Nikla,Benetti, Simonetta,Biondini, Gisella,De Risi, Carmela,Pollini, Gian P.
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p. 1373 - 1375
(2007/10/03)
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- A Simple Synthesis of Pyridine Aminophosphinic Acids and Pyridine Aminophosphine Oxides. The Unusual Cleavage of Pyridylmethyl-(N-benzylamino)-phenylphosphinic Acids and Phosphine Oxides in Acidic Solutions
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Pyridine aminophosphinic acids were synthesized in reaction, of N-(benzyl)-pyridylmethylimines with ethyl phenylphosphinate, in the presence of bromotrimethylsilane. Pyridine aminophosphine oxides were obtained in excellent yields by treatment of the corresponding imines with diphenylphosphine oxide. Among these compounds, the 2-pyridyl and 4-pyridyl derivatives were subject to a simple cleavage in aqueous mineral acid solutions. Products of the cleavages were N-(pyridylmethyl)benzylamines and phenylphosphonic (or diphenylphosphinic) acid, respectively.
- Boduszek, Bogdan
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p. 4087 - 4094
(2007/10/03)
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- The acidic cleavage of pyridylmethyl(amino)phosphonates. Formation of the corresponding amines
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Hydrolysis of 3-pyridylmethyl(amino)phosphonates by means of 20% aq. hydrochloric acid gave corresponding 3-pyridimethyl(amino)phosphonic acids, as expected. However, hydrolysis of 2- and 4-pyridylmethyl(amino)phosphonates led to decomposition of the phosphonates with a cleavage of C-P bond and formation of the corresponding amines. The leaving phosphorus moiety was identified as phosphoric acid. The scope of the reaction is limited to 2- and 4-pyridylmethyl derivatives of aminophosphonic acids and their esters, as well as to the derivatives possessing similar structure. On the contrary, the basic hydrolysis of 2- and 4-pyridylmethyl(amino)phosphonates led to the corresponding monoalkyl esters of the aminophosphonates, and no cleavage of C-P bond was observed in those cases.
- Boduszek, Bogdan
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p. 12483 - 12494
(2007/10/03)
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- 1-aminophosphonic acids and esters bearing heterocyclic moiety. Part 2. 1 pyridine, pyrrole and emidazole derivatives
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The benzylic amines (benzylamine, benzhydrylamine and benzyl carbamate) were applied in the synthesis of aminophosphonates derived from pyridine, pyrrole and imidazole. The Schiff bases obtained from corresponding heterocyclic aldehydes and benzylic amines were caused to react with diphenyl phosphorate or dibenzyl phosphonate to form corresponding heterocyclic aminophosphonates in good yields. The N-(benzylamino)-phosphonates were deblocked by catalytic hydrogenolysis. The benzhydryl group from the phosphonates was removed by acidic hydrolysis, and the carbobenzyloxy group from the phosphonates can be easy removed by treatment with a solution of 30% HBr in acetic acid, as well. It was found that during acidic hydrolysis of 2-and 4-pyridylmethylaminophosphonates a rearrangement occurred, combined with a cleavage of C-P bond in the phosphonate molecules and subsequent formation of the corresponding amines.
- Boduszek, Bogdan
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p. 209 - 218
(2007/10/03)
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- A simple, convenient and general method for the synthesis of N-acylalkylaminomethyl- and N-acylalkylamino(alkyl, aryl, heteroaryl)methylphosphonates and -phosphine oxides
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A variety of N-acylalkylaminomethyl- and alkylamino(alkyl, aryl, heteroaryl)methylphosphonates and -phosphine oxides has been efficiently prepared by acylation of suitable Schiff bases and subsequent treatment of the chloromethylcarboxamide intermediates with the appropriate phosphorylating agent.
- Couture,Deniau,Grandclaudon
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p. 953 - 956
(2007/10/02)
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- Asymmetric aza-Diels-Alder reaction: Enantio- and diastereoselective reaction of imine mediated by Chiral Lewis acid
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An efficient asymmetric aza-Diels-Alder reaction using chiral boron mediator is developed. The key to its success is the use of the chiral boron complex prepared in situ from (R)- or (S)- binaphthol and B(OPh)3. The enantiomeric reaction of prochiral imine affords products of up to 90% ee. The double asymmetric induction of chiral imine using α-benzylamine as a chiral auxiliary is achieved with almost complete diastereoselectivity for both aliphatic and aromatic aldimines. This method is applied to the efficient synthesis anabasine and coniine of piperidine alkaloides.
- Hattori, Kouji,Yamamoto, Hisashi
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p. 1749 - 1760
(2007/10/02)
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