4789-09-7Relevant academic research and scientific papers
Enantioconvergent Alkylations of Amines by Alkyl Electrophiles: Copper-Catalyzed Nucleophilic Substitutions of Racemic α-Halolactams by Indoles
Bartoszewicz, Agnieszka,Matier, Carson D.,Fu, Gregory C.
supporting information, p. 14560 - 14564 (2019/10/11)
Transition-metal catalysis has the potential to address shortcomings in the classic SN2 reaction of an amine with an alkyl electrophile, both with respect to reactivity and to enantioselectivity. In this study, we describe the development of a user-friendly method (reaction at room temperature, with commercially available catalyst components) for the enantioconvergent nucleophilic substitution of racemic secondary alkyl halides (α-iodolactams) by indoles. Mechanistic studies are consistent with the formation of a copper(I)-indolyl complex that reacts at different rates with the two enantiomers of the electrophile, which interconvert under the reaction conditions (dynamic kinetic resolution). This investigation complements earlier work on photoinduced enantioconvergent N-alkylation, supporting the premise that this important challenge can be addressed by a range of strategies.
Ruthenium-Pincer-Catalyzed Hydrogenation of Lactams to Amino Alcohols
Chen, Jiangbo,Wang, Jiaquan,Tu, Tao
, p. 2559 - 2565 (2018/07/30)
By using the commercially available ruthenium pincer complex (Ru-MACHO-BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value-added amino alcohols in good-to-excellent yields under mild reaction conditions. Remarkably, in addition to N-protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount of weak base or even under neutral reaction conditions, which further highlights the broad substrate scope and the protocol efficiency.
Visible-Light-Mediated Efficient Metal-Free Catalyst for α-Oxygenation of Tertiary Amines to Amides
Zhang, Yu,Riemer, Daniel,Schilling, Waldemar,Kollmann, Jiri,Das, Shoubhik
, p. 6659 - 6664 (2018/06/25)
A metal-free system has been discovered for the efficient α-oxygenation of tertiary amines to the corresponding amides using oxygen as an oxidant. This visible-light-mediated oxygenation reaction exhibited excellent substrates scope under mild reaction conditions and generated water as the only byproduct. The synthetic utility of this approach has been demonstrated by applying onto drug molecules. At the end, detailed mechanistic reactions clearly showed the role of oxygen and the photocatalyst.
Copper-Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amides
De, Subhadip,Yin, Junli,Ma, Dawei
supporting information, p. 4864 - 4867 (2017/09/23)
Cu2O/N,N′-bis(thiophen-2-ylmethyl)oxalamide is established to be an effective catalyst system for Goldberg amidation with inferior reactive (hetero)aryl chlorides, which have not been efficiently documented by Cu-catalysis to date. The reaction is well liberalized toward a variety of functionalized (hetero)aryl chlorides and a wide range of aromatic and aliphatic primary amides in good to excellent yields. Furthermore, the arylation of lactams and oxazolidinones is achieved. The present catalytic system also accomplished an intramolecular cross-coupling product.
PROCESS FOR THE PREPARATION OF APIXABAN AND INTERMEDIATES THEREOF
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Paragraph 0137, (2017/06/12)
The present invention refers to novel process for the preparation of Apixaban. Further, the invention also related to a process for the preparation of intermediate of Apixaban from very basic and cheap row material i.e. Aniline which is widely commercially available. The present invention provides process for preparation of Apixaban using a different sequence of synthetic steps and does not involve use of Ullmann reaction.
Copper(II) incorporated functionalized polystyrene catalyzed: N -arylation of amides under solvent free condition with broad substrate scope
Islam, Md. Mominul,Halder, Mita,Roy, Anupam Singha,Chatterjee, Sauvik,Bhaumik, Asim,Islam, Sk. Manirul
, p. 109692 - 109701 (2016/11/30)
We demonstrate here, a new polystyrene supported Cu(ii) catalyzed proficient synthetic methodology for the facile N-arylation of aromatic, aliphatic, cyclic and heterocyclic amides with aryl halides under neat conditions. The catalyst, PS-Cu(ii)-ala, was prepared through the grafting of copper metal on a polystyrene-β-alanine imine network. The catalyst shows a wide range of substrate scope and excellent functional group tolerance, and produces the desired anilides in mostly high yields. The material is thoroughly characterized by DRS-UV, FT-IR, AAS, FE-SEM, TGA analysis and energy dispersive X-ray (EDX) studies. The catalyst can be easily recovered from the reaction medium and reused without significant loss of its catalytic activity suggesting future potential of this catalyst.
A method of preparing intermediates [...]
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, (2017/01/23)
A disclosed preparation method for an apixaban intermediate comprises the following steps: step (1), performing an amidation reaction shown in the specification on a compound 3 and a compound M in an organic solvent under the effect of an organic alkali to obtain a reaction solution containing a compound 3'; and step (2), under the effect of an inorganic base, directly performing an nucleophilic substitution reaction shown in the specification on the reaction solution obtained in the step (1) to prepare a compound 4, and performing a nitration reaction on the compound 4 under the effect of concentrated sulfuric acid and concentrated nitric acid to prepare a compound 5. The preparation method provided by the invention is low in cost, simple in operation and suitable for industrialization.
CYCLIC AMIDES AS METAP-2 INHIBITORS
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Paragraph 0283; 0284; 0285; 0286; 0287; 0288; 0289, (2015/02/19)
Compounds of the formula (I), in which R1, R3, R5, R6, R7, R, X and Y have the meanings indicated in Claim 1, are inhibitors of methionine aminopeptidase and can be employed for the treatment of tumou
Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
supporting information, p. 474 - 478 (2014/01/23)
A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
Efficient ligand-free copper-catalyzed N-arylation of amides with aryl halides in water
Yong, Fui-Fong,Teo, Yong-Chua,Chua, Guan-Leong,Lim, Gina Shiyun,Lin, Yizhen
supporting information; experimental part, p. 1169 - 1172 (2011/03/21)
A convenient and efficient protocol has been developed for the cross-coupling of amides and aryl iodides using a ligand-free copper(I) oxide catalyst in water. A variety of amide derivatives afforded the corresponding N-arylated products in moderate to good yields (up to 88%).
