1492-13-3Relevant academic research and scientific papers
Photochemical Activation of Aromatic Aldehydes: Synthesis of Amides, Hydroxamic Acids and Esters
Nikitas, Nikolaos F.,Apostolopoulou, Mary K.,Skolia, Elpida,Tsoukaki, Anna,Kokotos, Christoforos G.
supporting information, p. 7915 - 7922 (2021/05/03)
A cheap, facile and metal-free photochemical protocol for the activation of aromatic aldehydes has been developed. Utilizing thioxanthen-9-one as the photocatalyst and cheap household lamps as the light source, a variety of aromatic aldehydes have been activated and subsequently converted in a one-pot reaction into amides, hydroxamic acids and esters in good to high yields. The applicability of this method was highlighted in the synthesis of Moclobemide, a drug against depression and social anxiety. Extended and detailed mechanistic studies have been conducted, in order to determine a plausible mechanism for the reaction.
Green Esterification of Carboxylic Acids Promoted by tert-Butyl Nitrite
Cheng, Xionglve,Jiang, Gangzhong,Li, Xingxing,Tao, Suyan,Wan, Xiaobing,Zhao, Yanwei,Zheng, Yonggao
supporting information, p. 2713 - 2718 (2021/06/25)
In this work, the green esterification of carboxylic acids promoted by tert-butyl nitrite has been well developed. This transformation is compatible with a broad range of substrates and exhibits excellent functional group tolerance. Various drugs and substituted amino acids are applicable to this reaction under near neutral conditions, with good to excellent yields.
Amidation of Aldehydes with Amines under Mild Conditions Using Metal-Organic Framework Derived NiO@Ni Mott-Schottky Catalyst
Goel, Bharat,Vyas, Ved,Tripathi, Nancy,Kumar Singh, Ajit,Menezes, Prashanth W.,Indra, Arindam,Jain, Shreyans K.
, p. 5743 - 5749 (2020/09/09)
Here we report a facile method for the synthesis of nickel oxide-nickel (NiO@Ni) Mott-Schottky catalyst employing metal-organic framework (MOF) as the precursor. A direct amidation protocol of aldehydes with amines has been optimized under mild conditions using NiO@Ni Mott-Schottky catalyst and it shows far better catalytic activity than the NiO?Ni nanoparticles prepared from simple Ni2+ salt under similar reaction conditions. The heterogeneous catalyst is robust, recyclable and efficient to provide comparable yield to costly ligand-based homogeneous Ni catalysts. The scope of the reaction protocol has been explored with variably substituted substrates. The reaction initiates by homolytic cleavage of peroxide and proceeds through radical mechanism.
Electrochemical anion pool synthesis of amides with concurrent benzyl ester synthesis
Mevan Dissanayake,Melville, Alex D.,Vannucci, Aaron K.
supporting information, p. 3165 - 3171 (2019/06/18)
An electrosynthesis method for amide bond formation has been developed in an attempt to increase the atom economy for this class of reactions. This "anion pool" method electrochemically generates strong nucleophiles from amine substrates. The amine nucleophiles then react with acid anhydrides to generate amides, and the by-product from this reaction undergoes further chemical transformations to generate pharmaceutically relevant benzoic esters. These one-pot reactions are operationally simple, are performed at room temperature, and avoid rare transition metals and added bases. The amide synthesis is amenable to primary and secondary amines and a variety of anhydrides with yields up to 90% obtained. Atom economy and process mass index (PMI) values calculated for this procedure indicate that this process can be considered greener compared to traditional amide synthesis routes used by industry. Furthermore, this electrochemical approach showed unique selectivity when substrates that contained two inequivalent amine moieties were examined.
Hydrogen Bond Directed ortho-Selective C?H Borylation of Secondary Aromatic Amides
Bai, Shao-Tao,Bheeter, Charles B.,Reek, Joost N. H.
supporting information, p. 13039 - 13043 (2019/07/31)
Reported is an iridium catalyst for ortho-selective C?H borylation of challenging secondary aromatic amide substrates, and the regioselectivity is controlled by hydrogen-bond interactions. The BAIPy-Ir catalyst forms three hydrogen bonds with the substrate during the crucial activation step, and allows ortho-C?H borylation with high selectivity. The catalyst displays unprecedented ortho selectivities for a wide variety of substrates that differ in electronic and steric properties, and the catalyst tolerates various functional groups. The regioselective C?H borylation catalyst is readily accessible and converts substrates on gram scale with high selectivity and conversion.
The: Ortho -substituent on 2,4-bis(trifluoromethyl)phenylboronic acid catalyzed dehydrative condensation between carboxylic acids and amines
Wang, Ke,Lu, Yanhui,Ishihara, Kazuaki
supporting information, p. 5410 - 5413 (2018/05/30)
2,4-Bis(trifluoromethyl)phenylboronic acid is a highly effective catalyst for dehydrative amidation between carboxylic acids and amines. Mechanistic studies suggest that a 2:2 mixed anhydride is expected to be the only active species, and the ortho-substituent of boronic acid plays a key role in preventing the coordination of amines to the boron atom of the active species, thus accelerating the amidation. This catalyst works for α-dipeptide synthesis.
Oxidative amidation of benzyl alcohols with amino acid esters mediated by N-hydroxysuccinimide/phenyliodine diacetate
Mahesh, Mandipogula,Panduranga, Veladi,Prabhu, Girish,Kumar L, Roopesh,Ramana, P. Venkata,Sureshbabu, Vommina V.
, p. 716 - 721 (2017/03/27)
A simple protocol involving metal-free oxidative amidation of benzyl alcohols with amino acid esters has been presented. The amidation proceeds in a radical pathway unlike in conventional metal-mediated extrusion of dihydrogen. The method is advantageous in terms of metal-free conditions, nonexpensive commercial starting substrates. Also various substituents in the starting materials are tolerated and sterically hindered amino acid side chains could provide good yields of amide products.
Boronic acid-DMAPO cooperative catalysis for dehydrative condensation between carboxylic acids and amines
Ishihara, Kazuaki,Lu, Yanhui
, p. 1276 - 1280 (2016/02/05)
Arylboronic acid and 4-(N,N-dimethylamino)pyridine N-oxide (DMAPO) cooperatively catalyse the dehydrative condensation reaction between carboxylic acids and amines to give the corresponding amides under azeotropic reflux conditions. This cooperative use is much more effective than their individual use as catalysts, and chemoselectively promotes the amide condensation of (poly)conjugated carboxylic acids. The present method is practical and scalable, and has been applied to the synthesis of sitagliptin and a drug candidate.
N-heterocyclic carbene-catalyzed oxidative amidation of aldehydes with amines
Alanthadka, Anitha,Maheswari, C. Uma
supporting information, p. 1199 - 1203 (2015/04/22)
The N-heterocyclic carbene (NHC)-catalyzed oxidative amidation of aromatic aldehydes with amines in the presence of N-bromosuccinimide (NBS) as an oxidant has been developed for the synthesis of amides. This amidation strategy is tolerant to both the electronic and the steric nature of the aryl aldehydes employed. The present methodology was extended to chiral amino acid derivatives to generate the corresponding amides in good yields and excellent ee values (>98%).
Magnetic CuFe2O4nanoparticles: A retrievable catalyst for oxidative amidation of aldehydes with amine hydrochloride salts
Suresh Kumar,Thulasiram,Bala Laxmi,Rawat, Vikas S.,Sreedhar
supporting information, p. 6059 - 6067 (2014/12/10)
The application of magnetic CuFe2O4nanoparticles for the oxidative amidation of aldehydes with amine hydrochloride salts is described. A wide range of amides have been synthesized in good to excellent yields under mild conditions. Chiral amide also synthesized from its corresponding chiral amine salt with retention of the stereochemistry. In particular, the performance of the magnetic separation of the catalyst was very efficient and an alternative to time, solvent and energy-consuming separation procedures. The catalytic activity of the catalyst remains unaltered after five consecutive cycles, making it environmentally benign and widely applicable due to its efficiency, ease of handling and cost effectiveness.
