4252-31-7Relevant academic research and scientific papers
Irreversible Inhibition of Mammalian and Insect Peptidylglycine &α-Hydroxylating Monooxygenases (PHMs), Peptide Amidating Enzymes, by N-Formyl Amides
Klinge, Michael,Cheng, Hengmiao,Zabriskie, T. Mark,Vederas, John C.
, p. 1379 - 1380 (1994)
A series of N-formyl amides were synthesized by condensation of N,N-bis(trimethylsilyl)formamide with acid chlorides (59-90percent yields), or by reaction of hydroxyglycyl peptides with 90percent hydrogen peroxide (45percent yield); a number of N-formyl amides which bear a phenyl substituent are mechanism-based irreversible inactivators of peptidylglycine α-hydroxylating monooxygenases purified from pig pituitary and from honeybee heads.
Epoxidation of Vinylamides by Dimethyldioxirane: First Spectral Evidence for Enamide Oxides
Adam, Waldemar,Reinhardt, Dirk,Reissig, Hans-Ulrich,Paulini, Klaus
, p. 12257 - 12262 (1995)
The oxidation of the (E)- and (Z)-N-propenylbenzamides (1) by dimethyldioxirane (DMD) in acetone solution leads to the α-amido epoxides 2, which were detected by low-temperature NMR spectroscopy; above -50 deg C they dimerize to the diastereomeric dioxane
An NHC-Stabilised Phosphinidene for Catalytic Formylation: A DFT-Guided Approach
Sreejyothi,Bhattacharyya, Kalishankar,Kumar, Shiv,Kumar Hota, Pradip,Datta, Ayan,Mandal, Swadhin K.
supporting information, p. 11656 - 11662 (2021/07/02)
In recent years, the applications of low-valent main group compounds have gained momentum in the field of catalysis. Owing to the accessibility of two lone pairs of electrons, NHC-stabilised phosphinidenes have been found to be excellent Lewis bases; however, they cannot yet be used as catalysts. Herein, an NHC-stabilised phosphinidene, 1,3-dimethyl-2-(phenylphosphanylidene)-2,3-dihydro-1H imidazole (1), for the activation of CO2 is reported.A closer inspection of the CO2 activation process by DFT calculations along with intrinsic bond orbital analysis shows that phosphinidene is associated with phenylsilane through a noncovalent π-π interaction between two phenyl rings which activates the Si?H bond facilitating hydride transfer to the CO2 molecule. Detailed DFT studies along with spectroscopic experiments were combined to understand the mechanism of CO2 activation and its catalytic reductive functionalisation leading to the formylation of a range of chemically inert primary amides under mild reaction conditions.
Immobilized Zn(OAc)2on bipyridine-based periodic mesoporous organosilica for N -formylation of amines with CO2and hydrosilanes
Lin, Xiao-Tao,Matsumoto, Kazuhiro,Maegawa, Yoshifumi,Takeuchi, Katsuhiko,Fukaya, Norihisa,Sato, Kazuhiko,Inagaki, Shinji,Choi, Jun-Chul
supporting information, p. 9501 - 9505 (2021/06/14)
Zinc acetate (Zn(OAc)2) was successfully immobilized on a bipyridine-based periodic mesoporous organosilica (BPy-PMO-TMS), as confirmed by solid-state NMR and energy-dispersive X-ray spectroscopies, X-ray diffractometry, and nitrogen adsorption/desorption isotherm analyses. The immobilized Zn complex, Zn(OAc)2(BPy-PMO-TMS), exhibited good catalytic activity during the N-formylations of amines and amides with CO2 and PhSiH3 to produce the corresponding formamides. Zn(OAc)2(BPy-PMO-TMS) with a lower Zn loading was found to exhibit higher catalytic activity.
Facile access to: N-formyl imide as an N-formylating agent for the direct synthesis of N-formamides, benzimidazoles and quinazolinones
Huang, Hsin-Yi,Liang, Chien-Fu,Lin, Xiu-Yi,Yen, Shih-Yao
supporting information, p. 5726 - 5733 (2020/08/21)
N-Formamide synthesis using N-formyl imide with primary and secondary amines with catalytic amounts of p-toluenesulfonic acid monohydrate (TsOH·H2O) is described. This reaction is performed in water without the use of surfactants. Moreover, N-formyl imide is efficiently synthesized using acylamidines with TsOH·H2O in water. In addition, N-formyl imide was successfully used as a carbonyl source in the synthesis of benzimidazole and quinazolinone derivatives. Notable features of N-formylation of amines by using N-formyl imide include operational simplicity, oxidant- A nd metal-free conditions, structurally diverse products, and easy applicability to gram-scale operation.
Designing a Cr-catalyst bearing redox non-innocent phenalenyl-based ligand towards hydrosilylative CO2functionalization
Chakraborty, Soumi,Das, Arpan,Ahmed, Jasimuddin,Barman, Sayani,Mandal, Swadhin K.
supporting information, p. 13788 - 13791 (2020/11/18)
Herein, we report the synthesis of a Cr(iii)-complex bearing a redox non-innocent phenalenyl-based ligand and its use as a catalyst for SET mediated hydrosilylative reduction of carbon dioxide towards formylation of primary amides under mild conditions. A
Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst
Zhang, Qiao,Lin, Xiao-Tao,Fukaya, Norihisa,Fujitani, Tadahiro,Sato, Kazuhiko,Choi, Jun-Chul
supporting information, p. 8414 - 8422 (2020/12/29)
A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.
One-Pot Anodic Conversion of Symmetrical Bisamides of Ethylene Diamine to Unsymmetrical gem-Bisamides of Methylene Diamine
Golub, Tatiana,Dou, Gui-Yuan,Zeng, Cheng-Chu,Becker, James Y.
supporting information, p. 7961 - 7964 (2019/10/11)
Symmetrical bisamides of ethylene diamine of type ArCONHCH2CH2NHCOAr undergo anodic C-C bond cleavage in acetonitrile-LiClO4 under controlled-potential electrolysis. The electrogenerated carbocation intermediates react with the solvent acetonitrile to afford unsymmetrical gem-bisamides of type ArCONHCH2NHCOMe in a one-pot reaction. The yields of the latter products are moderate (up to 60%). Other minor products involve two symmetrical gem-bisamides of type ArCONHCH2NHCOAr and MeCONHCH2NHCOMe and fragmentation products (e.g., ArCONHCHO, ArCONH2, and ArCN).
Mild and facile synthesis of formamide: Reduction and functionalization of CO2 using NaBH(OAc)3 under atmospheric pressure
Liu, Huan,Nie, Zhuang,Shao, Jiaan,Chen, Wenteng,Yu, Yongping
supporting information, p. 3552 - 3555 (2019/07/09)
An approach for N-formylation of amines was developed using NaBH(OAc)3 as a reductant under an atmospheric pressure of CO2 at 50 °C. The corresponding formylated products of various amines, including aliphatic and aromatic amines, amines with reductive-sensitive nitro groups and alkynyl groups and benzamides were obtained in good to excellent yields, and the possible reaction mechanism was also proposed.
Selective formylation or methylation of amines using carbon dioxide catalysed by a rhodium perimidine-based NHC complex
Lam, Raphael H.,McQueen, Caitlin M. A.,Pernik, Indrek,McBurney, Roy T.,Hill, Anthony F.,Messerle, Barbara A.
supporting information, p. 538 - 549 (2019/02/14)
Carbon dioxide can play a vital role as a sustainable feedstock for chemical synthesis. To be viable, the employed protocol should be as mild as possible. Herein we report a methodology to incorporate CO2 into primary, secondary, aromatic or alkyl amines catalysed by a Rh(i) complex bearing a perimidine-based NHC/phosphine pincer ligand. The periminide-based ligand belongs to a class of 6-membered NHC ligand accessed through chelate-assisted double C-H activation. N-Formylation and -methylation of amines were performed using a balloon of CO2, and phenylsilane as the reducing agent. Product selectivity between formylated and methylated products was tuned by changing the solvent, reaction temperature and the quantity of phenylsilane used. Medium to excellent conversions, as well as tolerance to a range of functional groups, were achieved. Stoichiometric reactions with reactants employed in catalysis and time course studies suggested that formylation and methylation reactions of interest begin with hydrosilylation of CO2 followed by reaction with amine substrates.
