Hydrogen atom transfer in metal ion complexes of the glutathione thiyl radical

2018 ◽  
Vol 429 ◽  
pp. 39-46 ◽  
Author(s):  
Michael Lesslie ◽  
Justin Kai-Chi Lau ◽  
Gardenia Pacheco ◽  
John T. Lawler ◽  
K.W. Michael Siu ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Metal Ion ◽  
Hydrogen Atom Transfer ◽  
Thiyl Radical ◽  
Atom Transfer ◽  
Metal Ion Complexes

Hydrogen atom transfer from 1,2- and 1,3-diols to the cumyloxyl radical. The role of structural effects on metal-ion induced C–H bond deactivation

2019 ◽  
Vol 55 (36) ◽  
pp. 5227-5230 ◽  
Author(s):  
Teo Martin ◽  
Michela Salamone ◽  
Massimo Bietti
Keyword(s):  
Hydrogen Atom ◽  
Metal Ion ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Structural Effects ◽  
Substrate Structure

Strong C–H bond deactivation toward HAT has been observed in the reactions of the cumyloxyl radical with 1,2- and 1,3-diols, following addition of Li+ and Ca2+. Weaker effects have been observed with Mg2+. The role of substrate structure and of the metal ion is discussed.

Using the Thiyl Radical for Aliphatic Hydrogen‐Atom Transfer: Thiolation of Unactivated C−H Bonds

2020 ◽  
Author(s):  
Liubov I. Panferova ◽  
Mikhail O. Zubkov ◽  
Vladimir A. Kokorekin ◽  
Vitalij V. Levin ◽  
Alexander D. Dilman
Keyword(s):  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Thiyl Radical ◽  
Atom Transfer

Using the Thiyl Radical for Aliphatic Hydrogen‐Atom Transfer: Thiolation of Unactivated C−H Bonds

2020 ◽  
Author(s):  
Liubov I. Panferova ◽  
Mikhail O. Zubkov ◽  
Vladimir A. Kokorekin ◽  
Vitalij V. Levin ◽  
Alexander D. Dilman
Keyword(s):  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Thiyl Radical ◽  
Atom Transfer

Reactions of alkoxy radicals. IV. Intramolecular hydrogen-atom transfer in the presence of cupric ion: A novel directive effect

1964 ◽  
Vol 17 (12) ◽  
pp. 1342 ◽  
Author(s):  
B Acott ◽  
ALJ Beckwith
Keyword(s):  
Hydrogen Atom ◽  
Metal Ion ◽  
Hydrogen Atom Transfer ◽  
Ferrous Ion ◽  
Atom Transfer ◽  
Unsaturated Alcohol ◽  
Alkoxy Radicals ◽  
Alkyl Radicals ◽  
Cupric Ion ◽  
Intramolecular Hydrogen

2-Methyl-2-hexyloxy radical (V), generated by ferrous-ion reduction of 2-methyl-2-hexyl hydroperoxide, undergoes intramolecular hydrogen-atom transfer to the extent of 44%, yielding 2-hydroxy-2-methyl-5-hexyl radical (XIII). Oxidation of the latter with cupric ion in acetic acid affords a mixture of 2-methyl-4-hexen-2-ol (XXI) and 2-methyl-5-hexen-2-ol (XX). Similar results were obtained using radicals derived from 2,5-dimethyl-2-hexyl hydroperoxide and 2-methyl-2-heptyl hydroperoxide. In each case the preponderant formation of the unsaturated alcohol having an olefinic link in the δ-position with respect to the hydroxy group demonstrates the operation of a novel directive effect, for which a possible mechanism is discussed. Some other examples of metal-ion oxidation of alkyl radicals are described. No product arising from intramolecular hydrogen-atom transfer was isolated from ferrous-ion reduction of 2,4,4-trimethyl-2-pentyl hydroperoxide.

Alkali-Metal-Ion-Assisted Hydrogen Atom Transfer in the Homocysteine Radical

2016 ◽  
Vol 22 (7) ◽  
pp. 2243-2246 ◽  
Author(s):  
Michael Lesslie ◽  
Justin Kai-Chi Lau ◽  
John T. Lawler ◽  
K. W. Michael Siu ◽  
Jos Oomens ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Alkali Metal ◽  
Metal Ion ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Alkali Metal Ion

Metal-Ion Influence on Ligand-Centered Hydrogen-Atom Transfer

2021 ◽  
Vol 60 (3) ◽  
pp. 1579-1589
Author(s):  
Bronte J. Charette ◽  
Joseph W. Ziller ◽  
Alan F. Heyduk
Keyword(s):  
Hydrogen Atom ◽  
Metal Ion ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer

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