Reductive cleavage mechanism of diphenyl ether and apparent ipso trapping of an intermediate radical anion with a silyl ether

1982 ◽  
Vol 47 (22) ◽  
pp. 4250-4254 ◽  
Author(s):  
Kundanbhai M. Patel ◽  
Richard J. Baltisberger ◽  
Virgil I. Stenberg ◽  
Neil F. Woolsey
Keyword(s):  
Radical Anion ◽  
Diphenyl Ether ◽  
Reductive Cleavage ◽  
Silyl Ether ◽  
Intermediate Radical

scholarly journals Electro-mediated PhotoRedox Catalysis for Selective C(sp3)-O Cleavages of Phosphinates to Carbanions

2021 ◽  
Author(s):  
Xianhai Tian ◽  
Tobias Karl ◽  
Sebastian Reiter ◽  
Shahboz Yakubov ◽  
Regina de Vivie-Riedle ◽  
...  
Keyword(s):  
Radical Anion ◽  
Reductive Cleavage ◽  
Photoredox Catalysis ◽  
Structural Variations ◽  
Aryl Chlorides ◽  
Anion Form

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp<sup>3</sup>)-O bonds of phosphinates to alkyl carbanions. As well as deoxygenations, olefinations are reported which are <i>E</i>-selective and can be made <i>Z</i>-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for a more intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp<sup>3</sup>)-O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions i) tolerate aryl chlorides/bromides and ii) do not give rise to Birch-type reductions.

Colchicine red-ox chemistry revisited: Cathodic behavior and EPR observation of an intermediate radical anion

Tetrahedron ◽  
1999 ◽  
Vol 55 (38) ◽  
pp. 11601-11608 ◽  
Author(s):  
Marino Cavazza ◽  
Lamberto Nucci ◽  
Elisa Pannocchia ◽  
Lucio Pardi ◽  
Francesco Pergola ◽  
...  
Keyword(s):  
Radical Anion ◽  
Intermediate Radical

A kinetic study of the reductive cleavage of diphenyl ether by sodium in liquid ammonia

1989 ◽  
Vol 54 (1) ◽  
pp. 261-262 ◽  
Author(s):  
Robert R. Dewald ◽  
Nora J. Conlon ◽  
Woo M. Song
Keyword(s):  
Kinetic Study ◽  
Liquid Ammonia ◽  
Diphenyl Ether ◽  
Reductive Cleavage

scholarly journals Electro-mediated PhotoRedox Catalysis for Selective C(sp3)-O Cleavages of Phosphinates to Carbanions

2021 ◽  
Author(s):  
Xianhai Tian ◽  
Tobias Karl ◽  
Sebastian Reiter ◽  
Shahboz Yakubov ◽  
Regina de Vivie-Riedle ◽  
...  
Keyword(s):  
Radical Anion ◽  
Reductive Cleavage ◽  
Photoredox Catalysis ◽  
Structural Variations ◽  
Aryl Chlorides ◽  
Anion Form

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp<sup>3</sup>)-O bonds of phosphinates to alkyl carbanions. As well as deoxygenations, olefinations are reported which are <i>E</i>-selective and can be made <i>Z</i>-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for a more intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp<sup>3</sup>)-O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions i) tolerate aryl chlorides/bromides and ii) do not give rise to Birch-type reductions.

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