scholarly journals A radical rebound mechanism for the methane oxidation reaction promoted by the dicopper center of a pMMO enzyme: a computational perspective

2016 ◽  
Vol 45 (6) ◽  
pp. 2492-2504 ◽  
Author(s):  
Júlio C. S. Da Silva ◽  
Robert C. R. Pennifold ◽  
Jeremy N. Harvey ◽  
Willian R. Rocha
Keyword(s):  
Hydrogen Atom ◽  
Triplet State ◽  
Methane Oxidation ◽  
Oxidation Reaction ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Binuclear Copper ◽  
Copper Site ◽  
Computational Perspective

Hydrogen Atom Transfer (HAT) promoted by a triplet state of the bis-oxoCu2(iii) core generates a new radical rebound mechanism for the hydroxylation of methane catalyzed by the binuclear copper site of a pMMO enzyme.

scholarly journals Triplet state promoted reaction of SO2 with H2O by competition between proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) processes

2019 ◽  
Vol 21 (19) ◽  
pp. 9779-9784 ◽  
Author(s):  
Josep M. Anglada ◽  
Marilia T. C. Martins-Costa ◽  
Joseph S. Francisco ◽  
Manuel F. Ruiz-López
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Triplet State ◽  
Electronic State ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Excited Triplet ◽  
Proton Coupled Electron Transfer

The excited triplet electronic state of SO2 (a3B1) reacts with water through a proton coupled electron transfer (pcet) mechanism rather than via a conventional hydrogen atom transfer (hat) process.

Direct Cyclization of Alkenyl Thioester via Transition Metal‐hydrogen Atom Transfer/radical‐polar Crossover Mechanism

2019 ◽  
Author(s):  
Shiori Date ◽  
Kensei Hamasaki ◽  
Karen Sunagawa ◽  
Hiroki Koyama ◽  
Chikayoshi Sebe ◽  
...  
Keyword(s):  
Natural Products ◽  
Hydrogen Atom ◽  
Transition Metal ◽  
Hydrogen Atom Transfer ◽  
Synthetic Method ◽  
Atom Transfer ◽  
Reaction Conditions ◽  
Hydride Hydrogen ◽  
Sulfur Heterocycles ◽  
One Step

<div>We report here a catalytic, Markovnikov selective, and scalable synthetic method for the synthesis of saturated sulfur heterocycles, which are found in the structures of pharmaceuticals and natural products, in one step from an alkenyl thioester. Unlike a potentially labile alkenyl thiol, an alkenyl thioester is stable and easy to prepare. The powerful Co catalysis via a cobalt hydride hydrogen atom transfer and radical-polar crossover mechanism enabled simultaneous cyclization and deprotection. The substrate scope was expanded by the extensive optimization of the reaction conditions and tuning of the thioester unit.</div>

Catalytic Synthesis of Cyclic Guanidines via Hydrogen Atom Transfer and Radical-Polar Crossover

2020 ◽  
Author(s):  
Shunya Ohuchi ◽  
Hiroki Koyama ◽  
Hiroki Shigehisa
Keyword(s):  
Hydrogen Atom ◽  
Functional Group ◽  
Hydrogen Atom Transfer ◽  
Catalytic Synthesis ◽  
Membered Ring ◽  
Biologically Active ◽  
Atom Transfer ◽  
Powerful Method ◽  
Protective Groups ◽  
The Common

A catalytic synthesis of cyclic guanidines, which are found in many biologically active compounds and natu-ral products, was developed, wherein transition-metal hydrogen atom transfer and radical-polar crossover were employed. This mild and functional-group tolerant process enabled the cyclization of alkenyl guanidines bearing common protective groups, such as Cbz and Boc. This powerful method not only provided the common 5- and 6-membered rings but also an unusual 7-membered ring. The derivatization of the products afforded various heterocycles. We also investigated the se-lective cyclization of mono-protected or hetero-protected (TFA and Boc) alkenyl guanidines and their further derivatiza-tions.

Sign in / Sign up

Export Citation Format

Share Document