Nonaromatic aminium radicals

Chow, Yuan L.; Danen, Wayne C.; Nelsen, Stephen F.; Rosenblatt, David H.

doi:10.1021/cr60313a003

Cited by 241 publications

(161 citation statements)

References 67 publications

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“…Using an adaptation of the method of Treinin and Hayon (7), for the process one can predict that the charge transfer transition should occur near 250 nm. 4 The computations therefore support the charge transfer character of the transition observed in the low pH region of aqueous NH3" (9).…”

Section: Nh3'+supporting

confidence: 57%

“…They are also prototypes of the nitrogen-centered organic amino radicals that occur in numerous organic and biochemical systems (4,5 ) , and their reactions are of interest in corrosion chemistry (6). In aqueous solution, NH2' radicals can be made in reaction [ l ] [I]…”

Section: Introductionmentioning

confidence: 99%

“…In Sect. 4, the results are used in a critical examination of the thermodynamic and redox properties, and the UV-visible absorption spectra of NH2' and NH3'+ in aqueous solution. General conclusions are summarized in Sect.…”

Section: Introductionmentioning

confidence: 99%

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Gas and solution phase thermochemistry and transition energies of NH₂^• and NH₃^•+, and their aquo complexes: an ab initio study

Yu¹,

Rauk²

1994

Can. J. Chem.

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DAKE Yu, ARVI RAUK and DAVID A. ARMSTRONG. Can. J. Chem. 72, 471 (1994). IAb i n~t~o calculations were performed on several aquo complexes of NH,', and NH3'+, and on monomeric parent species. The geometries were optimized at the HF16-31+G* level and the vibrational frequencies were calculated. The total energies and the binding energies of complexes were evaluated at the MP216-31+G* + ZPE level of theory. Gas and aqueous solution phase thermodynamic properites of NH,' and NH3'+ and several other species were calculated. The examination of solution phase properties of the radicals was facilitated by study of the structures and transition energies of aquo complexes. H- [Traduit par la rCdaction]

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Section: Nh3'+supporting

confidence: 57%

Section: Introductionmentioning

confidence: 99%

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Gas and solution phase thermochemistry and transition energies of NH₂^• and NH₃^•+, and their aquo complexes: an ab initio study

Yu¹,

Rauk²

1994

Can. J. Chem.

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“…L'imonium (1) est Cgalernent form6 en sCrie aniline et est caractCrisC non seulement par I'obtention de I'amine secondaire 'Une discussion de ces rCactions est donnCe dans une revue rCcente (8 Le rkarrangement en hydrolyxamines 7 (a partir de 5) et 13 (a partir de 10) observC pour la premiere fois sur des N-oxydes serait dC 2 un mCcanisme radicalaire analogue a celui intervenant sur les sels d'ammonium quaternaires soumis 2 l'action des bases (RCaction de Stevens) (9,10).…”

Section: Monodeprotonationunclassified

Deprotonation de N-oxydes d'amines aliphatiques: schéma réactionnel général et nouvelle synthèse de pyrrolidines

Beugelmans¹,

Benadjila-Iguertsira²,

Chastanet³

et al. 1985

Can. J. Chem.

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Amine oxides, 1, 5, 10, 15, 21, 23, when treated by lithium diisopropylamide undergo deprotonation. Monodeprotonation gives rise either to secondary amines and benzaldehyde resulting from the hydrolysis of an intermediate immonium (I) or to hydroxylamines via a Stevens-like rearrangement observed for the first time on an amine oxide. Double deprotonation gives an immonium ylid (Y) which, depending upon the structure of the initial tertiary amine yields either "head to head" piperazines (biradical-like behavior of (DD)) or aziridines. The immonium ylid (Y5) derived from trimethylamine oxide, whose formation and reactivity are reported for the first time, has the remarkable property of undergoing cycloaddition reactions with unactivated olefins, leading to a new and efficient synthesis of various pyrrolidines.

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“…It was argued that the SSIP formed between 1,4-dicyanonaphthalene (DCN) and t-amine after initial one electron exchange, in a solvent of high dielectric constant, would dissociate into free radical ion pair (FRIP) where the cyanoarene anion radical would be potentially less reactive towards the amino cation radical. Predominant deprotonation from these amino cation radicals in aqueous solvent would result an α-amino radical and molecular oxygen dissolved in the solvent would quench the cyanoarene anion radical to its original ground state, possibly making it available for a second oxidation step from α-amino radical similar to the electrolytic oxidation 17 of amines as shown in Fig. 1.…”

Section: Introductionmentioning

confidence: 99%

Sequential two electron photooxidation of t-amines: generation of a regiospecific iminium cation and its application in organic synthesis

Pandey¹,

Gadre²

2003

Arkivoc

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PET activation of cyclic t-amines, utilizing 9, 10-dicyanonaphthalene (DCN) as light absorbing electron acceptor in aqueous acetonitrile solution, leads to the generation of iminium cation intermediate involving electron -proton -electron (E-P-E) transfer sequence. Iminium cation generation is found to be highly regiospecific and depends upon the kinetic acidity which is subject to the stereoelectronic factor of the α -C-H proton of the unymmetrical t-amines. Tetrahydro-1, 3-oxazines (6) are synthesized in complete regio-and stereoselective manner from the PET activation of the substrates of type 4. Nucleophilic alkylation of 6 by alkyl Grignard reagents provides cis-α, α'-dialkyl cyclic amines (8). Similarly, chiral perhydropyrido[2,1-b][1, 3, 4]-oxadiazinone (11) is synthesized as a precursor for the synthesis of optically active α-alkyl piperidines. Both enantiomers of hemlock alkaloid coniine (13) are also synthesized. Furthermore, to broaden the scope of these reactions, precursor 16 is designed for the synthesis of various α -amino acids and their N-alkyl derivatives.

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Nonaromatic aminium radicals

Cited by 241 publications

References 67 publications

Gas and solution phase thermochemistry and transition energies of NH₂^• and NH₃^•+, and their aquo complexes: an ab initio study

Gas and solution phase thermochemistry and transition energies of NH₂^• and NH₃^•+, and their aquo complexes: an ab initio study

Deprotonation de N-oxydes d'amines aliphatiques: schéma réactionnel général et nouvelle synthèse de pyrrolidines

Sequential two electron photooxidation of t-amines: generation of a regiospecific iminium cation and its application in organic synthesis

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Nonaromatic aminium radicals

Cited by 241 publications

References 67 publications

Gas and solution phase thermochemistry and transition energies of NH2• and NH3•+, and their aquo complexes: an ab initio study

Gas and solution phase thermochemistry and transition energies of NH2• and NH3•+, and their aquo complexes: an ab initio study

Deprotonation de N-oxydes d'amines aliphatiques: schéma réactionnel général et nouvelle synthèse de pyrrolidines

Sequential two electron photooxidation of t-amines: generation of a regiospecific iminium cation and its application in organic synthesis

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Gas and solution phase thermochemistry and transition energies of NH₂^• and NH₃^•+, and their aquo complexes: an ab initio study

Gas and solution phase thermochemistry and transition energies of NH₂^• and NH₃^•+, and their aquo complexes: an ab initio study