N,N ‘-Dimethyl-N,N ‘-diarylurea Anion Radicals:  An Intramolecular Reductive Elimination

The one-electron reduction of tertiary N,N ‘-dimethyl-N,N ‘-diarylureas (aryl = phenyl, β-naphthyl, α-naphthyl), in HMPA, results in anion radicals that undergo novel intramolecular reductive elimination reactions leading to the formation of the anion radicals of the corresponding biaryls. These res...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2003-02, Vol.125 (6), p.1460-1461
Main Authors: Kurth, Todd L., Lewis, Frederick D., Hattan, Chris M., Reiter, Richard C., Stevenson, Cheryl D.
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Free radicals chemistry
Organic chemistry
Reactivity and mechanisms
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Summary:The one-electron reduction of tertiary N,N ‘-dimethyl-N,N ‘-diarylureas (aryl = phenyl, β-naphthyl, α-naphthyl), in HMPA, results in anion radicals that undergo novel intramolecular reductive elimination reactions leading to the formation of the anion radicals of the corresponding biaryls. These results are due to face to face π−π stacking interactions involving the two aromatic rings in the urea systems. The overlapping p π orbitals on the ipso carbons of opposing aryl groups evolve into a σ bond leading to the formation of the biaryl anion radical. In the case of the N,N‘-dimethyl-N,N‘-di-2-pyrenylurea system, there is a node in the LUMO of the number 2 carbon, and the parent anion radical remains intact.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0291890