scholarly journals Hydrogen Atom Transfer Reaction Free Energy as a Predictor of Abiotic Nitroaromatic Reduction Rate Constants: A Comprehensive Analysis

2020 ◽  
Vol 39 (9) ◽  
pp. 1678-1684
Author(s):  
Dominic M. Di Toro ◽  
Kevin P. Hickey ◽  
Herbert E. Allen ◽  
Richard F. Carbonaro ◽  
Pei C. Chiu
Keyword(s):  
Free Energy ◽  
Hydrogen Atom ◽  
Rate Constants ◽  
Transfer Reaction ◽  
Reduction Rate ◽  
Hydrogen Atom Transfer ◽  
Comprehensive Analysis ◽  
Atom Transfer ◽  
Reaction Free Energy

Experimental Validation of Hydrogen Atom Transfer Gibbs Free Energy as a Predictor of Nitroaromatic Reduction Rate Constants

2019 ◽  
Vol 53 (10) ◽  
pp. 5816-5827 ◽  
Author(s):  
Jimmy Murillo-Gelvez ◽  
Kevin P. Hickey ◽  
Dominic M. Di Toro ◽  
Herbert E. Allen ◽  
Richard F. Carbonaro ◽  
...  
Keyword(s):  
Free Energy ◽  
Hydrogen Atom ◽  
Gibbs Free Energy ◽  
Rate Constants ◽  
Experimental Validation ◽  
Reduction Rate ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer

Sulfamides Direct Radical-Mediated Chlorination of Aliphatic C–H Bonds

2019 ◽  
Author(s):  
Melanie Short ◽  
Mina Shehata ◽  
Matthew Sanders ◽  
Jennifer Roizen
Keyword(s):  
Hydrogen Atom ◽  
Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Chain Propagation ◽  
Propagation Mechanism ◽  
Atom Transfer ◽  
Radical Chain ◽  
Radical Intermediates ◽  
Transfer Processes ◽  
Unusual Position

Sulfamides guide intermolecular chlorine transfer to gamma-C(sp<sup>3</sup>) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage in otherwise rare 1,6-hydrogen-atom transfer processes. The disclosed chlorine-transfer reaction relies on a light-initiated radical chain-propagation mechanism to oxidize C(sp<sup>3</sup>)-H bonds.

Sulfamides Direct Radical-Mediated Chlorination of Aliphatic C–H Bonds

2019 ◽  
Author(s):  
Melanie Short ◽  
Mina Shehata ◽  
Matthew Sanders ◽  
Jennifer Roizen
Keyword(s):  
Hydrogen Atom ◽  
Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Chain Propagation ◽  
Propagation Mechanism ◽  
Atom Transfer ◽  
Radical Chain ◽  
Radical Intermediates ◽  
Transfer Processes ◽  
Unusual Position

Sulfamides guide intermolecular chlorine transfer to gamma-C(sp<sup>3</sup>) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage in otherwise rare 1,6-hydrogen-atom transfer processes. The disclosed chlorine-transfer reaction relies on a light-initiated radical chain-propagation mechanism to oxidize C(sp<sup>3</sup>)-H bonds.

Hydrogen Atom Transfer Reaction Free Energy as a Predictor of Abiotic Nitroaromatic Reduction Rate Constants: A Comprehensive Analysis

2019 ◽  
Author(s):  
Dominic Di Toro ◽  
Kevin P. Hickey ◽  
Herbert E. Allen ◽  
Richard F. Carbonaro ◽  
Pei C. Chiu
Keyword(s):  
Free Energy ◽  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Energy Model ◽  
Second Order ◽  
Transfer Model ◽  
Atom Transfer ◽  
Order Rate ◽  
Linear Free Energy ◽  
Free Energy Model

<div>A linear free energy model is presented that predicts the second order rate constant for the abiotic reduction of nitroaromatic compounds (NACs). For this situation previously presented models use the one electron reduction potential of the NAC reaction. If such value is not available, it has been has been proposed that it could be computed directly or estimated from the electron affinity (EA). The model proposed herein uses the Gibbs free energy of the hydrogen atom transfer (HAT) as the parameter in the linear free energy model. Both models employ quantum chemical computations for the required thermodynamic parameters. The available and proposed models are compared using second order rate constants obtained from five investigations reported in the literature in which a variety of NACs were exposed to a variety of reductants. A comprehensive analysis utilizing all the NACs and reductants demonstrate that the computed hydrogen atom transfer model and the experimental one electron reduction potential model have similar root mean square errors and residual error probability distributions. In contrast, the model using the computed electron affinity has a more variable residual error distribution with a significant number of outliers. The results suggest that a linear free energy model utilizing computed hydrogen transfer reaction free energy produces a more reliable prediction of the NAC abiotic reduction second order rate constant than previously available methods. The advantages of the proposed hydrogen atom transfer model and its mechanistic implications are discussed as well.</div>

Hydrogen-atom transfer reaction from triplet 2-naphthylammonium ion to ground-state aromatic ketones

1983 ◽  
Vol 101 (6) ◽  
pp. 598-602 ◽  
Author(s):  
Haruo Shizuka ◽  
Masaru Fukushima
Keyword(s):  
Hydrogen Atom ◽  
Ground State ◽  
Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Aromatic Ketones

Intramolecular 1,5-hydrogen atom transfer reaction promoted by phosphoramidyl and carbamoyl radicals: synthesis of 2-amino-C-glycosides

2007 ◽  
Vol 48 (36) ◽  
pp. 6384-6388 ◽  
Author(s):  
Cosme G. Francisco ◽  
Antonio J. Herrera ◽  
Ángeles Martín ◽  
Inés Pérez-Martín ◽  
Ernesto Suárez
Keyword(s):  
Hydrogen Atom ◽  
Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer

ChemInform Abstract: Generation of Glycinyl Radicals via a 1,5-Hydrogen Atom Transfer Reaction. Applications to γ-Lactam Formation.

ChemInform ◽  
2010 ◽  
Vol 29 (43) ◽  
pp. no-no
Author(s):  
J. RANCOURT ◽  
V. GORYS ◽  
E. JOLICOEUR
Keyword(s):  
Hydrogen Atom ◽  
Transfer Reaction ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer
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