Competitive Hydrogen Atom Transfer to Oxyl- and Peroxyl Radicals in the Cu-Catalyzed Oxidative Coupling of N-Aryl Tetrahydroisoquinolines Using tert-Butyl Hydroperoxide

ACS Catalysis ◽  
2016 ◽  
Vol 6 (5) ◽  
pp. 3253-3261 ◽  
Author(s):  
Esther Boess ◽  
Larry M. Wolf ◽  
Santanu Malakar ◽  
Michela Salamone ◽  
Massimo Bietti ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Oxidative Coupling ◽  
Hydrogen Atom Transfer ◽  
Peroxyl Radicals ◽  
Atom Transfer ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

scholarly journals Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer

2018 ◽  
Vol 14 ◽  
pp. 2259-2265 ◽  
Author(s):  
Xiaoshen Ma ◽  
Seth B Herzon
Keyword(s):  
Hydrogen Atom ◽  
Alkyl Radical ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Radical Intermediate ◽  
Butyl Hydroperoxide ◽  
Tert Butyl Hydroperoxide ◽  
Starting Point ◽  
Reductive Couplings ◽  
Complex Settings

We show that cobalt bis(acetylacetonate) [Co(acac)2], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et3SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformations are believed to proceed by cobalt-mediated hydrogen atom transfer (HAT) to the alkene substrate, followed by interception of the resulting alkyl radical intermediate with a SOMOphile. In addition, we report the first reductive couplings of unactivated alkenes and aryldiazonium salts by an HAT pathway. The simplicity and generality of the Co(acac)2–TBHP–Et3SiH reagent combination suggests it as a useful starting point to develop HAT reactions in complex settings.

scholarly journals α-Acetoxyarone synthesis via iodine-catalyzed and tert-butyl hydroperoxide-mediateded self-intermolecular oxidative coupling of aryl ketones

2017 ◽  
Vol 13 ◽  
pp. 1079-1084 ◽  
Author(s):  
Liquan Tan ◽  
Cui Chen ◽  
Weibing Liu
Keyword(s):  
Oxidative Coupling ◽  
Optimum Conditions ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Radical Intermediates ◽  
Tert Butyl Hydroperoxide ◽  
Aryl Ketones

We present a metal-free method for α-acetoxyarone synthesis by self-intermolecular oxidative coupling of aryl ketones using I2−tert-butyl hydroperoxide (TBHP). Under the optimum conditions, various aryl ketones gave the corresponding products in moderate to excellent yields. A series of control experiments were performed; the results suggest the involvement of radical pathways. Multiple radical intermediates were generated in situ and the overall process involved several different reactions, which proceeded self-sequentially in a single reactor. A labeling experiment using 18O-labeled H2O confirmed that the oxygen in the product was derived from TBHP, not from H2O in the TBHP solvent.

Photoelectron spectroscopy, gas phase acidity, and thermochemistry of tert-butyl hydroperoxide: Mechanisms for the rearrangement of peroxyl radicals

1998 ◽  
Vol 109 (23) ◽  
pp. 10293-10310 ◽  
Author(s):  
Eileen P. Clifford ◽  
Paul G. Wenthold ◽  
Roustam Gareyev ◽  
W. Carl Lineberger ◽  
Charles H. DePuy ◽  
...  
Keyword(s):  
Gas Phase ◽  
Photoelectron Spectroscopy ◽  
Peroxyl Radicals ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Gas Phase Acidity ◽  
Tert Butyl Hydroperoxide

Green oxidant H2O2 as a hydrogen atom transfer reagent for visible light-mediated Minisci reaction

2019 ◽  
Vol 43 (32) ◽  
pp. 12533-12537 ◽  
Author(s):  
Hong Zhao ◽  
Zhenlong Li ◽  
Jian Jin
Keyword(s):  
Hydrogen Atom ◽  
Visible Light ◽  
Oxidative Coupling ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Metal Free

A metal-free protocol for oxidative coupling of heteroarenes and aliphatic C–H components has been achieved via a radical pathway.

Metal-Free Oxidative Coupling of Tetrahydroisoquinolines and 3-Fluorooxindoles on Water

Synthesis ◽  
2019 ◽  
Vol 52 (03) ◽  
pp. 471-478
Author(s):  
Jian Ji ◽  
Ling-Yan Chen ◽  
Zi-Bin Qiu ◽  
Xinfeng Ren ◽  
Ya Li
Keyword(s):  
Oxidative Coupling ◽  
Reaction Conditions ◽  
Butyl Hydroperoxide ◽  
Metal Free ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

An efficient, metal-free oxidative coupling of tetrahydroisoquinolines and 3-fluorooxindoles on water has been developed. Using aqueous tert-butyl hydroperoxide as the oxidant, Et3N as the base, and water as the sole solvent, a variety of 3-fluorooxindoles fully substituted at the 3-position and containing a tetrahydroisoquinoline fragment has been successfully prepared in yields of up to 93% with an anti/syn stereo­selectivity of up to 99:1 under very mild and safe reaction conditions.

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