3555-72-4Relevant academic research and scientific papers
Oxidation-Cope elimination: A REM-resin cleavage protocol for the solid-phase synthesis of hydroxylamines
Sammelson, Robert E,Kurth, Mark J
, p. 3419 - 3422 (2001)
We have established that using an oxidation-Cope elimination cleavage protocol allows for the synthesis of N,N-disubstituted hydroxylamines from REM resin (polymer-bound benzyl acrylate). Michael addition of a secondary amine or addition of a primary amine followed by reductive alkylation provides polymer-bound tertiary amines. Oxidation of these resin-bound tertiary amines with MCPBA is followed by concomitant Cope elimination to regenerate the polymer-bound acrylate and provide the cleaved hydroxylamines.
Synthesis of N,N,O-Trisubstituted Hydroxylamines by Stepwise Reduction and Substitution of O-Acyl N,N-Disubstituted Hydroxylamines
Dhanju, Sandeep,Crich, David
supporting information, p. 1820 - 1823 (2016/05/19)
Diverse N,N,O-trisubstituted hydroxylamines, an under-represented group in compound collections, are readily prepared by partial reduction of N-acyloxy secondary amines with diisobutylaluminum hydride followed by acetylation and reduction of the so-formed O-acyl-N,N-disubstituted hydroxylamines with triethylsilane and boron trifluoride etherate. Use of carbon nucleophiles in the last step, including allyltributylstannane, silyl enol ethers, and 2-methylfuran, gives N,N,O-trisubstituted hydroxylamines with branching α- to the O-substituent. N,N-Disubstiuted hydroxylamines are conveniently prepared by reaction of secondary amines with dibenzoyl peroxide followed by diisobutylaluminum hydride reduction.
The Reactivity of Difluorocarbene with Hydroxylamines: Synthesis of Carbamoyl Fluorides
Baars, Hannah,Engel, Julien,Mertens, Lucas,Meister, Daniela,Bolm, Carsten
, p. 2293 - 2299 (2016/07/29)
Carbamoyl fluorides are formed in reactions of hydroxylamines with difluorocarbene generated from sodium bromodifluoroacetate as readily available and non-toxic carbene precursor. The process shows a high functional group tolerance, and the reaction path has been rationalized by computational calculations. (Figure presented.) .
Oxidation of secondary amines by molecular oxygen and cyclohexanone monooxygenase
Colonna, Stefano,Pironti, Vincenza,Carrea, Giacomo,Pasta, Piero,Zambianchi, Francesca
, p. 569 - 575 (2007/10/03)
Cyclohexanone monooxygenase from Acinetobacter calcoaceticus catalyzed the oxidation of tertiary and secondary amines to N-oxides and nitrones, respectively. The formation of a hydroxylamine intermediate was involved with secondary amines as starting substrates.
Oxidation of amines catalyzed by cyclohexanone monooxygenase
Colonna, Stefano,Pironti, Vincenza,Pasta, Piero,Zambianchi, Francesca
, p. 869 - 871 (2007/10/03)
Cyclohexanone monooxygenase catalyzed the oxidation of tertiary, secondary and hydroxylamines to N-oxides, hydroxylamines and nitrones respectively.
A novel oxidative transformation of α-aminonitriles to amides
Yokoshima, Satoshi,Kubo, Tetsuji,Tokuyama, Hidetoshi,Fukuyama, Tohru
, p. 122 - 123 (2007/10/03)
A novel oxidative transformation of α-aminonitriles to amides is reported. Oxidation of α-aminonitriles with peracid, followed by basic treatment affords, amides in good yields. A mechanistic aspect of this transformation is also discussed.
Nitrogen inversion and N-O bond rotation in some hydroxylamine and isoxazolidine derivatives
Hassan, Azfar,Wazeer, Mohamed I. M.,Perzanowski, Herman P.,Ali, Sk. Asrof
, p. 411 - 418 (2007/10/03)
A series of trisubstituted hydroxylamine derivatives, both cyclic and acyclic, has been prepared. The energy barriers in these hydroxylamines are found to be dominated either by nitrogen inversion or N-O bond rotation depending on the nature of the substi
Origin of "Hetero Effect" on Nitrogen Inversion. Comparison of Hydroxylamines and Aminoxide Anions
Perrin, Charles L.,Thoburn, John D.,Elsheimer, Seth
, p. 7034 - 7038 (2007/10/02)
Rate constants for nitrogen inversion in N-benzyl-N-methylhydroxylamine, N,N-diethylhydroxylamine, 1-hydroxy-2,2,4,4-tetramethylpyrrolidine, their conjugate bases, and their O-acetyl derivatives in dimethylformamide-d7 were determined based on the 1H NMR
Metalloenzyme Models. Divalent Metal Ion Catalyzed Hydrolysis of p-Nitrophenyl Picolinate in the Presence of Imidazoles and Pyridines Having Hydroxyl Groups in Their Side Chains
Ogino, Kenji,Shindo, Katsuhiko,Minami, Tooru,Tagaki, Waichiro,Eiki, Toshio
, p. 1101 - 1106 (2007/10/02)
Rate constants for hydrolysis of p-nitrophenyl picolinate at 25 deg C in the pH range 6.5-8.5 were measured in the absence and presence of divalent metal ions (Ni(II), Zn(II), Co(II), Ca, Mg) and substituted imidazoles or pyridines as ligands having alcoholic hydroxyl groups in their side chains. In the presence of either metal ion or ligand, the rate is slow and the pseudo-first-order rate constant (kobsd) increases linearly in a first-order manner with respect to the concentration of metal ion or ligand until it gives the second-order rate constant, kM or kL, respectively. In the presence of both a metal ion (Ni(II) or Zn(II)) and a ligand, rate increase is remarkable for some ligands and the increase in kobsd values constructs saturation curves with respect to increase in either metal ion or ligand concentration. The saturation curves were analyzed based upon rate equations formulated by assuming the formation of 1:1 complex of metal ion and ligands as the catalyst, leading to evaluation of the association constant K for complexes and the second-order rate constant kc for the reaction of complex with substrate. Values of kobsd, kc, and K are dependent greatly upon the structure of ligands and pH. The ligands complexed with Zn(II) ion appear to be simple but highly active models of hydrolytic metalloenzymes.
