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

Frederick D Lewis; Tong Ing Ho; J. Thomas Simpson

doi:10.1021/jo00319a007

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

Chemistry

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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 language	English (US)
Pages (from-to)	1077-1082
Number of pages	6
Journal	Journal of Organic Chemistry
Volume	46
Issue number	6
DOIs	https://doi.org/10.1021/jo00319a007
State	Published - Jan 1 1981

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Organic Chemistry

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title = "Photochemical Addition of Tertiary Amines to Stilbene. Stereoelectronic Control of Tertiary Amine Oxidation",

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.",

author = "Lewis, {Frederick D} and Ho, {Tong Ing} and {Thomas Simpson}, J.",

year = "1981",

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T1 - Photochemical Addition of Tertiary Amines to Stilbene. Stereoelectronic Control of Tertiary Amine Oxidation

AU - Lewis, Frederick D

AU - Ho, Tong Ing

AU - Thomas Simpson, J.

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Y1 - 1981/1/1

N2 - 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.

AB - 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.

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

Abstract

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