A Radical-Anion Chain Mechanism Initiated by Dissociative Electron Transfer to a Bicyclic Endoperoxide: Insight into the Fragmentation Chemistry of Neutral Biradicals and Distonic Radical Anions

2008 ◽  
Vol 14 (6) ◽  
pp. 1698-1709 ◽  
Author(s):  
David C. Magri ◽  
Mark S. Workentin
Keyword(s):  
Electron Transfer ◽  
Radical Anion ◽  
Radical Anions ◽  
Chain Mechanism ◽  
Dissociative Electron Transfer ◽  
Fragmentation Chemistry ◽  
Insight Into

Paramagnetic organometallic molecules. XIV. Ion-pair and steric effects in dissociative electron transfer reactions of metal cluster carbonyl radical anions

1983 ◽  
Vol 36 (3) ◽  
pp. 441 ◽  
Author(s):  
CM Kirk ◽  
BM Peake ◽  
BH Robinson ◽  
J Simpson
Keyword(s):  
Electron Transfer ◽  
Metal Cluster ◽  
Metal Carbonyl ◽  
Electron Attachment ◽  
Transfer Reactions ◽  
Organic Radical ◽  
Radical Anions ◽  
Dissociative Electron Attachment ◽  
Dissociative Electron Transfer ◽  
Electron Transfer Reactions

An investigation of electron attachment reactions of cluster metal carbonyls is presented. In general, alkyl and organometallic halides react rapidly with metal carbonyl cluster radical anions at ambient temperatures to give the neutral cluster molecule. Halide ion and alkyl or organometallic radicals are also produced, which indicate that these are dissociative electron attachment reactions analogous to those of organic radical anions. The rate of dissociative electron attachment in reactions of PhCCo3(CO)9- was found to depend on the R-X bond energy, the size of the alkyl group and the nature of the counter-ion. In particular, (Ph3P)2N+ retarded some electron transfer reactions to the extent that the bimolecular decay of PhCCo3(CO)9- effectively competed with the electron transfer process in determining the reaction path.

Electron-Transfer-Induced Intramolecular Heck Carbonylation Reactions Leading to Benzolactones and Benzolactams

Synthesis ◽  
2018 ◽  
Vol 50 (15) ◽  
pp. 3015-3021 ◽  
Author(s):  
Ilhyong Ryu ◽  
Takahide Fukuyama ◽  
Takanobu Bando
Keyword(s):  
Carbon Monoxide ◽  
Electron Transfer ◽  
Nucleophilic Attack ◽  
Metal Catalyst ◽  
Radical Anions ◽  
Chain Mechanism ◽  
Benzyl Alcohols ◽  
Carbonylation Reaction ◽  
Catalyst Free ◽  
Acyl Radicals

A metal-catalyst-free intramolecular Heck carbonylation reaction of benzyl alcohols and benzyl amines with carbon monoxide under heating at 250 °C affords the corresponding benzolactones and benzolactams in good to excellent yields. A hybrid radical/ionic chain mechanism, involving electron transfer from radical anions generated by nucleophilic attack of alcohols or amines on intermediate acyl radicals, is proposed.

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