1906-82-7Relevant academic research and scientific papers
Hydrogenolysis of geminal diazides
Biallas, Phillip,Kirsch, Stefan F.
, p. 4209 - 4211 (2017)
The complete hydrogenolysis of compounds containing the geminal diazido functionality is described. Using hydrogen over palladium on charcoal, the diazides are reduced, and primary amines are obtained. For example, aminomalonates and glycines are generated in a straightforward manner. A protocol that provides direct access to acetylated amines derived from 2-amino-1,3-diketones in good to excellent yields, via hydrogenation in the presence of acetic anhydride, is also presented.
Iridium porphyrin catalyzed N-H insertion reactions: Scope and mechanism
Anding, Bernie J.,Woo, L. Keith
, p. 2599 - 2607 (2013/06/26)
Ir(TTP)CH3 catalyzed N-H insertion reactions between ethyl diazoacetate (EDA) or methyl phenyldiazoacetate (MPDA) and a variety of aryl, aliphatic, primary, and secondary amines to generate substituted glycine esters with modest to high yields. Aniline substrates generally gave yields above 80%, with up to 105 catalyst turnovers, and without slow addition of the diazo reagent. Good yields were also achieved with aliphatic amines, though higher catalyst loadings and slow addition of the amine were necessary in some cases. Primary amines reacted with EDA to generate both single- and double-insertion products, either of which could be produced selectively in high yield with the proper choice of stoichiometric ratios and reaction temperature. Notably, mixed trisubstituted amines, RN(CH2CO2Et) (CHPhCO2Me), were generated from the insertion of 1 equiv of EDA and 1 equiv of MPDA into primary amines. The N-H insertion mechanism was examined using substrate competition studies, trapping experiments, and multiple spectroscopic techniques. Substrate competition studies using pairs of amines with EDA or MPDA revealed Hammett correlations with respective slopes of ρ = 0.15 and ρ+ = -0.56 as well as kinetic isotope ratios of k H/kD = 1.0 ± 0.2 and 2.7 ± 0.2. Competitive amine binding to the iridium center was demonstrated by kinetics and equilibrium binding studies. Equilibrium binding constants ranged from 102 to 105. Monitoring the reaction by absorption spectroscopy revealed a transient metalloporphyrin complex. The lifetime of this species was dependent on the nature of the amine substrate, which suggests that the catalytic cycle proceeds through a metal-ylide intermediate.
Chemoselectivity in coupling of azides with thioacids in solution-phase and solvent-free conditions
Nagarajan, Sangaraiah,Shanmugavelan, Poovan,Sathishkumar, Murugan,Priyadharshini, Namachivayam,Sudakar, Padmanaban,Ponnuswamy, Alagusundaram
, p. 668 - 680 (2013/01/15)
Solvent-free rapid coupling of monothiocarboxylic acid with azide affords carboxamide chemoselectively. Triphenyl phosphine included as an additive influences the chemoselectivity, yielding carboxamide and thioamide. Similar variation in the chemoselectivity is observed in the absence and presence of triphenyl phosphine in solution-phase methodology. Rapidity and ecofriendliness of the solvent-free approach to yield the products in just 15min is noteworthy compared to the solution-phase protocol, which has a long reaction time (1-3 days).
Copper-exchanged bentonite: A reusable catalysis for the formation of alkoxycarbonyl nitrile ylides under microwave irradiation
Bendedouche, Choukri Kamel,Benhaoua, Hadj
experimental part, p. 149 - 151 (2012/10/18)
Ethyldiazoacetate reacts as a carbene precursor in presence of copper exchanged bentonite. Reaction with excess nitrile gave oxazole derivatives. Their formation is explained by intramolecular 1,5-cyclisation of alkoxycarbonyl substituted nitrile ylide intermediate.
Functionalizing glycine derivatives by direct C-C bond formation
Zhao, Liang,Li, Chao-Jun
supporting information; experimental part, p. 7075 - 7078 (2009/04/07)
(Chemical Equation Presented) Come on glycine: Two different types of glycine derivatives are α-functionalized using cross-dehydrogenative- coupling (CDC) reactions. The method allows the efficient attachment of a malonate or aromatic alkyne group on the α-position of the glycine derivatives under very mild conditions.
ANTI-ODOR COMPOSITIONS AND THERAPEUTIC USE
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, (2008/06/13)
This application discloses a composition comprising a malodor compound and an anti-odor ingredient effective for reducing the presence or production of malodor. The composition may be topically applied to a subject and is useful for cosmetic conditions, pharmaceutical indications, or other objectives.
Competitive formation of 10- and 7-membered hydrogen-bonded rings of proline-containing model peptides
Jin, Yusuke,Tonan, Kenji,Ikawa, Shun-Ichi
, p. 2795 - 2802 (2007/10/03)
Intramolecularly hydrogen-bonded structures of proline-containing model peptides with a sequence of N-tert-butoxycarbonyl-prolyl-Xaa-NHCH3 [Xaa = Gly (glycyl), Ala (alanyl), Phe (phenylalanyl), Leu (leucyl), Ile (isoleucyl), and Val (valyl)] were studied by proton nuclear magnetic resonance and infrared spectroscopy. Variation of chemical shifts of amide protons with composition change of DMSO-d6/CDCl3 mixed solvents were found to be a good measure of intramolecular hydrogen bonding of peptides in CDCl3 solution. It has been shown that 10- and 7-membered hydrogen-bonded rings, which should have the β- and γ-turn like structures in proteins, respectively, form competitively with each other. It is suggested that the equilibrium between the two hydrogen-bonded rings is determined by steric hindrance due to a side chain of the Xaa residue. Free energies for formation of the 10- and 7-membered hydrogen-bonded rings, ΔG10 and ΔG7, were estimated from the solvent composition-dependent change of the chemical shifts. A good correlation between ΔG10 and the occurrence frequencies of residues Xaa at the (i + 2)th position for the β-turns in proteins has been found.
Synthesis of oxazoles and thiazoles using thioimidates
Yokoyama,Menjo,Watanabe,Togo
, p. 1467 - 1470 (2007/10/02)
Several oxazoles and thiazoles were synthesized easily by the reaction of N-(methylthioalkylidene)glycine ethyl ester with diethyl oxalate, acid halides, and thionesters in the presence of base.
Acylation de l'acetamidomalonate de diethyle. Synthese et reactivite du 4-ethoxycarbonyl oxazole
Loupy, Andre,Petit, Alain,Zaparucha, Anne,Mahieu, Claude,Semeria, Didier
, p. 642 - 647 (2007/10/02)
The acylation of diethyl acetamidomalonate by palmitoyl chloride was performed using KOtBu in THF.Subsequent reaction of acylmalonate with DMSO or NMP led to ethyl 5-alkyloxazole-4-carboxylate (global yield 76percent for the two steps).Some original reactions of this heterocycle are presented, including ring opening of oxazole. - Keywords: amphiphilic compounds / Krapcho reaction / trans-acylation / oxazoles
