The formation of radicals in the mitsunobu reaction

Camp, David, Hanson, Graeme R. and Jenkins, Ian D. (1995) The formation of radicals in the mitsunobu reaction. Journal of Organic Chemistry, 60 10: 2977-2980. doi:10.1021/jo00115a011

Author Camp, David
Hanson, Graeme R.
Jenkins, Ian D.
Title The formation of radicals in the mitsunobu reaction
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
Publication date 1995-05
Sub-type Article (original research)
DOI 10.1021/jo00115a011
Volume 60
Issue 10
Start page 2977
End page 2980
Total pages 4
Place of publication Washington, D.C. U.S.A.
Publisher American Chemical Society
Language eng
Subject 030501 Free Radical Chemistry
Abstract The first step of the Mitsunobu reaction, involving the reaction of triphenylphosphine with diisopropyl (or diethyl) azodicarboxylate, results in the formation of a radical cation. The EPR spectra of the N-centered radicals reveal hyperfine coupling to two nitrogen nuclei, a phosphorus nucleus, and one or two protons from the alkyl CH (or CH2) groups. The radical is relatively persistent, slowly decomposing at room temperature over a period of about 6 h. When the reaction was carried out in the presence of neopentyl alcohol (1 equiv), the radical still formed. However, in the presence of benzoic acid (1 equiv) or neopentyl alcohol/benzoic acid, no EPR signal was observed. This suggests that the order of addition of reagents in the Mitsunobu reaction may influence the outcome in some cases. A new mechanism, involving single electron transfer, is proposed for the formation of the Morrison-Brunn-Huisgen betaine. © 1995 American Chemical Society.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Centre for Advanced Imaging Publications
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