24167-56-4Relevant articles and documents
BICYCLIC PYRIDINE COMPOSITIONS AND METHODS OF USING THE SAME FOR CANCER THERAPY
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Page/Page column 50, (2020/08/22)
Disclosed herein are bicyclic pyridines, such as thienopyridine, pyrrolopyridine, furopyridine compounds, and methods for treating cancers. The method may comprise administering a therapeutically effective amount of any of the compositions described herei
Synthesis of secondary and tertiary amides without coupling agents from amines and potassium acyltrifluoroborates (KATs)
Bode, Jeffrey W.,Ryan, Sarah J.,Schuhmacher, Anne,Shiro, Tomoya
, p. 7609 - 7614 (2020/08/14)
Although highly effective for most amide syntheses, the activation of carboxylic acids requires the use of problematic coupling reagents and is often poorly suited for challenging cases such as N-methyl amino acids. As an alternative to both secondary and tertiary amides, we report their convenient synthesis by the rapid oxidation of trifluoroborate iminiums (TIMs). TIMs are easily prepared by acid-promoted condensation of potassium acyltrifluoroborates (KATs) and amines and are cleanly and rapidly oxidized to amides with hydrogen peroxide. The overall transformation can be conducted either as a one-pot procedure or via isolation of the TIM. The unique nature of the neutral, zwitterionic TIMs makes possible the preparation of tertiary amides via an iminium species that would not be accessible from other carbonyl derivatives and can be conducted in the presence of unprotected functional groups including acids, alcohols and thioethers. In preliminary studies, this approach was applied to the late-stage modifications of long peptides and the iterative synthesis of short, N-methylated peptides without the need for coupling agents.
Direct Synthesis of Amides from Oxidative Coupling of Benzyl Alcohols and N-substituted Formamides Using a Co–Al Based Heterogeneous Catalyst
Subhedar, Dnyaneshwar D.,Gupta, Shyam Sunder R.,Bhanage, Bhalchandra M.
, p. 3102 - 3111 (2018/08/21)
Present work reports the direct synthesis of amides from oxidative coupling of benzyl alcohols with various N-substituted formamides using a cobalt-hydrotalcite (Co-HT) derived catalyst. The Co-HT derived catalysts (Co-HT-2, Co-HT-3 and Co-HT-4 having Co2+/Al3+ molar ratio in the catalyst preparation mixture as 1/1, 2/1 and 3/1 respectively) were prepare following a co-precipitation method and characterized well by powder XRD, XPS, FEG-SEM, EDS, DTG–TGA, FT-IR and N2 physisorption measurements. A range of functional amides were obtained in good yields from oxidative coupling of various substituted benzyl alcohols and a range of N-substituted formamides using Co-HT-3 catalyst and oxidant TBHP. Mechanistic investigation suggests that the amidation reaction is associated with the formation and coupling of radical species. Furthermore, the Co-HT derived catalyst was easily recoverable and recyclable with retained high catalytic activity towards the oxidative coupling of benzyl alcohol with DMF. Graphical Abstract: [Figure not available: see fulltext.].
Oxidative amidation of benzaldehydes and benzylamines with: N -substituted formamides over a Co/Al hydrotalcite-derived catalyst
Gupta, Shyam Sunder R.,Nakhate, Akhil V.,Rasal, Kalidas B.,Deshmukh, Gunjan P.,Mannepalli, Lakshmi Kantam
, p. 15268 - 15276 (2017/12/15)
The present work describes a highly efficient synthetic strategy for amides via oxidative coupling of benzaldehydes or benzylamines with N-substituted formamides using a heterogeneous Co/Al hydrotalcite-derived catalyst in the presence of TBHP. A series of Co/Al hydrotalcite-derived catalysts (Cat-2, Cat-3, and Cat-4 with the Co2+/Al3+ molar ratio in the synthesis mixture as 1/1, 2/1 and 3/1) have been prepared by a simple co-precipitation method and characterized using powder XRD, XPS, FEG-SEM, EDS, FT-IR, DTG-TGA and N2 physical adsorption techniques. Among the as-prepared catalysts, Cat-3 exhibited excellent catalytic activity towards the direct amidation of benzaldehydes as well as benzylamines bearing various substituents into the corresponding amides at 100 °C using TBHP as an oxidant. The mechanistic investigation of the amidation reaction revealed that the reaction follows a radical pathway. Furthermore, the catalyst is easily separable and recyclable without considerable loss in catalytic activity.
Nucleophilic deoxyfluorination of phenols via aryl fluorosulfonate intermediates
Schimler, Sydonie D.,Cismesia, Megan A.,Hanley, Patrick S.,Froese, Robert D.J.,Jansma, Matthew J.,Bland, Douglas C.,Sanford, Melanie S.
, p. 1452 - 1455 (2017/02/10)
This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SO2F2) and tetramethylammonium fluoride (NMe4F) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMe4F proceeds under mild conditions (often at room temperature) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SO2F2 and NMe4F. Ab initio calculations suggest that carbon-fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.
METHOD FOR AROMATIC FLUORINATION
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Paragraph 0047-0049, (2017/12/18)
Disclosed is a fluorination method comprising providing an aryl fluorosuifonate and a fluorinating reagent to a reaction mixture; and reacting the aryl fluorosuifonate and the fluorinating reagent to provide a fluorinated aryl species. Also disclosed is a fluorination method comprising providing, a salt comprising a cation and an aryloxyiate, and SO2F2 to a reaction mixture; reacting the SO2F2 and the ammonium salt to provide a fluorinated aryl species. Further disclosed a fluorination method comprising providing a compound having the structure Ar-OH to a reaction mixture; where A is an aryl or heteroaryl; providing SO2F2 to the reaction mixture; providing a fluorinating reagent to the reaction mixture; reacting the SO2F2, the fluorinating reagent and the compound having the structure Ar-OH to provide a fluorinated aryl species having the structure Ar-F.
Copper-catalyzed amide bond formation from formamides and carboxylic acids
Liu, Hong-Qiang,Liu, Jun,Zhang, Yang-Hui,Shao, Chang-Dong,Yu, Jing-Xun
, p. 11 - 14 (2015/01/30)
A highly efficient copper-catalyzed approach to form amide bonds from formamides and carboxylic acids was developed. This protocol shows broad substrate scopes and high yields in the presence of 1 mol% catalyst and 4.0 equiv. formamides.
Potassium tert-Butoxide-Mediated Amine Acyl Exchange Reaction of N,N-Disubstituted Formamides with Aromatic Carbonyl Derivatives via Sequential C-N Bond Cleavage/Formation: An Approach to Aromatic Amides
Zhang, Ming-Zhong,Guo, Qing-Hu,Sheng, Wen-Bing,Guo, Can-Cheng
, p. 2855 - 2861 (2015/09/28)
A novel potassium tert-butoxide-mediated amine acyl exchange of N,N-disubstituted formamides with aromatic carbonyl derivatives in a sequential C-N bond cleavage/formation process leading to aromatic amides is described. This methodology tolerates a wide range of aromatic carbonyl compounds, including aromatic aldehydes, acyl chlorides, unactivated esters, and acid anhydrides. The usage of inexpensive and readily available reagents, broad substrate scope, and the simple, mild (50°C) and transition metal-free conditions make this protocol very practical. In addition, a plausible reaction mechanism is proposed on the basis of experimental observations.
Easy access to amides through aldehydic C-H bond functionalization catalyzed by heterogeneous Co-based catalysts
Bai, Cuihua,Yao, Xianfang,Li, Yingwei
, p. 884 - 891 (2015/02/19)
A novel synthesis strategy for amides by oxidative amidation of aldehydes is developed using a heterogeneous Co-based catalyst. The Co composite was prepared by simple pyrolysis of a Co-containing MOF, to obtain well-dispersed Co nanoparticles enclosed by carbonized organic ligands. The catalysts were characterized by powder X-ray diffraction (PXRD), N2 physical adsorption, atomic absorption spectroscopy (AAS), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The small Co nanoparticles embedded in the N-doped carbons were highly dispersed with an average size of ca. 7 nm. The Co@C-N materials exhibited significantly enhanced catalytic activity in the oxidative amidation of aldehydes in comparison to those of commercial sources. A series of amides can be easily obtained in good to excellent yields. It was found that the reaction proceeded via radicals under mild conditions, and the carbonyl group in the amide product was from the aldehyde. Moreover, the catalyst could be easily separated by using an external magnetic field and reused several times without significant loss in catalytic efficiency under the investigated conditions. (Chemical Equation Presented).
PhenoFluorMix: Practical chemoselective deoxyfluorination of phenols
Fujimoto, Teppei,Ritter, Tobias
supporting information, p. 544 - 547 (2015/03/05)
A practical deoxyfluorination with novel deoxyfluorinating reagent PhenoFluorMix, a mixture of N,N'-1,3-bis(2,6-diisopropylphenyl)chloroimidazolium chloride and CsF, is presented. PhenoFluorMix overcomes the challenges associated with hydrolysis of PhenoFluor. PhenoFluorMix does not hydrolyze, is readily available on decagram scale, and is storable in air. In this paper, we demonstrate the practicality of the reagent and exhibit the deoxyfluorination of a variety of phenols and heterocycles.
