- Reusable Co-nanoparticles for general and selectiveN-alkylation of amines and ammonia with alcohols
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A general cobalt-catalyzedN-alkylation of amines with alcohols by borrowing hydrogen methodology to prepare different kinds of amines is reported. The optimal catalyst for this transformation is prepared by pyrolysis of a specific templated material, which is generatedin situby mixing cobalt salts, nitrogen ligands and colloidal silica, and subsequent removal of silica. Applying this novel Co-nanoparticle-based material, >100 primary, secondary, and tertiary amines includingN-methylamines and selected drug molecules were conveniently prepared starting from inexpensive and easily accessible alcohols and amines or ammonia.
- Beller, Matthias,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kadam, Ravishankar G.,Li, Xinmin,Ma, Zhuang,Petr, Martin,Zbo?il, Radek,Zhou, Bei
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p. 111 - 117
(2022/01/06)
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- Cine-Silylative Ring-Opening of α-Methyl Azacycles Enabled by the Silylium-Induced C-N Bond Cleavage
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Described herein is the development of a borane-catalyzed cine-silylative ring-opening of α-methyl azacycles. This transformation involves four-step cascade processes: (i) exo-dehydrogenation of alicyclic amine, (ii) hydrosilylation of the resultant enamine, (iii) silylium-induced cis-β-amino elimination to open the ring skeleton, and (iv) hydrosilylation of the terminal olefin. The present borane catalysis also works efficiently for the C-N bond cleavage of acyclic tertiary amines. On the basis of experimental and computational studies, the silicon atom was elucidated to play a pivotal role in the β-amino elimination step.
- Zhang, Jianbo,Chang, Sukbok
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p. 12585 - 12590
(2020/08/21)
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- Alkylation of Amines Via Tandem Hydroaminomethylation Using Imino-Pyridine Complexes of Rhodium as Catalyst Precursors
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Abstract: Novel cationic Rh(I) imino-pyridine complexes were evaluated as catalyst precursors in the hydroaminomethylation of 1-octene in conjunction with both primary (aniline and benzylamine) and secondary amines (piperidine). These complexes were found
- October, Jacquin,Mapolie, Selwyn F.
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p. 998 - 1010
(2019/11/03)
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- Biocatalytic N-Alkylation of Amines Using Either Primary Alcohols or Carboxylic Acids via Reductive Aminase Cascades
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The alkylation of amines with either alcohols or carboxylic acids represents a mild and safe alternative to the use of genotoxic alkyl halides and sulfonate esters. Here we report two complementary one-pot systems in which the reductive aminase (RedAm) from Aspergillus oryzae is combined with either (i) a 1° alcohol/alcohol oxidase (AO) or (ii) carboxylic acid/carboxylic acid reductase (CAR) to affect N-alkylation reactions. The application of both approaches has been exemplified with respect to substrate scope and also preparative scale synthesis. These new biocatalytic methods address issues facing alternative traditional synthetic protocols such as harsh conditions, overalkylation and complicated workup procedures.
- Ramsden, Jeremy I.,Heath, Rachel S.,Derrington, Sasha R.,Montgomery, Sarah L.,Mangas-Sanchez, Juan,Mulholland, Keith R.,Turner, Nicholas J.
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supporting information
p. 1201 - 1206
(2019/01/21)
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- Benzylamines via Iron-Catalyzed Direct Amination of Benzyl Alcohols
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Benzylamines play a prominent role in numerous pharmaceutically active compounds. Thus, the development of novel, sustainable catalytic methodologies to provide access to these privileged structural motifs is of central importance. Herein we describe a systematic study for the construction of a large variety of benzylamines using a well-defined homogeneous iron complex. The methodology consists of the direct coupling of readily available benzyl alcohols with simpler amines through the borrowing hydrogen methodology, producing a variety of substituted secondary and tertiary benzylamines in moderate to excellent yields for the first time with an iron catalyst. Notably, we explore the versatility of this methodology in the one-pot synthesis of nonsymmetric tertiary amines, sequential functionalization of diols with distinctly different amines, and the synthesis of N-benzyl piperidines via various synthetic pathways. In addition, direct conversion of the renewable building block 2,5-furan-dimethanol to pharmaceutically relevant compounds is achieved.
- Yan, Tao,Feringa, Ben L.,Barta, Katalin
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p. 381 - 388
(2016/01/12)
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- Discovery of a metalloenzyme-like cooperative catalytic system of metal nanoclusters and catechol derivatives for the aerobic oxidation of amines
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We have discovered a new class of cooperative catalytic system, consisting of heterogeneous polymer-immobilized bimetallic Pt/Ir alloyed nanoclusters (NCs) and 4-tert-butylcatechol, for the aerobic oxidation of amines to imines under ambient conditions. After optimization, the desired imines were obtained in good to excellent yields with broad substrate scope. The reaction rate was determined to be first-order with respect to the substrate and catechol and zero-order for the alloyed Pt/Ir NC catalyst. Control studies revealed that both the heterogeneous NC catalyst and 4-tert-butylcatechol are essential and act cooperatively to facilitate the aerobic oxidation under mild conditions.
- Yuan, Hao,Yoo, Woo-Jin,Miyamura, Hiroyuki,Kobayashi, Shu
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supporting information
p. 13970 - 13973
(2012/10/29)
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- A general and selective copper-catalyzed reduction of secondary amides
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In situ-generated cationic copper/pybox catalyst systems allow for the selective reduction of secondary amides into the corresponding amines under mild conditions. This novel protocol has a wide substrate scope and shows good functional group tolerance. The Royal Society of Chemistry 2012.
- Das, Shoubhik,Join, Benoit,Junge, Kathrin,Beller, Matthias
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supporting information; experimental part
p. 2683 - 2685
(2012/04/04)
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- Methods of producing pantothenic acid derivative and its starting materials for producing the same
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A method of producing a pantothenic acid derivative of formula (I): STR1 wherein each of R1 and R2 is different, and is a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, or a phenyl group; or a straight chain aliphat
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- THE CHEMISTRY OF BENZOTRIAZOLE. PART 8. A NOVEL TWO-STEP PROCEDURE FOR THE N-ALKYLATION OF AMIDES
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Benzotriazole, aldehydes RCHO, and amides R1CONH2 react together with elimination of water to form 1:1:1 adducts which are reduced smoothly by NaBH4 to give the N-substituted amides R1CONHCH2R.Both steps occur in high yields and can be carried out on a large scale, thus comprising a convenient general method for the N-alkylation of amides.
- Katritzky, Alan R.,Drewniak, Malgorzata
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p. 2339 - 2344
(2007/10/02)
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