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. In: Proceedings of: Gordon Research Conference on Free Radical Reactions. Gordon Research Conference on Free Radical Reactions, Holderness, NH, U.S.A., (2977-2980). 16-21 July 1995. doi:10.1021/jo00115a011

Author Camp, David
Hanson, Graeme R.
Jenkins, Ian D.
Title of paper The Formation of radicals in the Mitsunobu reaction
Conference name Gordon Research Conference on Free Radical Reactions
Conference location Holderness, NH, U.S.A.
Conference dates 16-21 July 1995
Proceedings title Proceedings of: Gordon Research Conference on Free Radical Reactions   Check publisher's open access policy
Journal name Journal of Organic Chemistry   Check publisher's open access policy
Publication Year 1995
DOI 10.1021/jo00115a011
ISBN not found
ISSN 0022-3263
Volume 60
Issue 10
Start page 2977
End page 2980
Total pages not found
Language eng
Formatted Abstract/Summary
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 alcoho/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
Subjects 0305 Organic Chemistry
030501 Free Radical Chemistry
030606 Structural Chemistry and Spectroscopy
0306 Physical Chemistry (incl. Structural)
Additional Notes Presented as "P12". Proceedings not found. Abstract reproduced from J. Org. Chem., 1995, 60 (10), 2977-2980, the previous month: see DOI in Links section.

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Created: Thu, 22 Jul 2010, 14:26:18 EST by Jon Swabey on behalf of Faculty of Science