Photochemical Addition of Tertiary Amines to Stilbene. Stereoelectronic Control of Tertiary Amine Oxidation

Frederick D Lewis*, Tong Ing Ho, J. Thomas Simpson

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

95 Scopus citations

Abstract

The photochemical addition reactions of seven nonsymmetrical tertiary amines with singlet trans-stilbene are described. Addition of methyldiisopropylamine or isopropyldimethylamine is highly selective for formation of the least substituted α-amino radical, whereas addition of several less highly branched amines is relatively nonselective. The product isotope effect for tert-butylmethyl(trideuteriomethyl)amine is 2.2 ± 0.2. Product selectivity is determined by the orientation of deprotonation of an aminium radical intermediate by the stilbene radical anion. Selective oxidation results from a stereoelectronic effect which is most evident when one or more alkyl group is highly branched.

Original languageEnglish (US)
Pages (from-to)1077-1082
Number of pages6
JournalJournal of Organic Chemistry
Volume46
Issue number6
DOIs
StatePublished - Jan 1 1981

ASJC Scopus subject areas

  • Organic Chemistry

Fingerprint Dive into the research topics of 'Photochemical Addition of Tertiary Amines to Stilbene. Stereoelectronic Control of Tertiary Amine Oxidation'. Together they form a unique fingerprint.

Cite this