Homolytic aziridine opening (aza variant of cyclopropylcarbinyl-homoallyl rearrangement) by addition of tributyltin radical to N-acylaziridines. Factors contributing to the regioselectivity

Jürgen Werrya, Helmut Stamm, Pen Yuan Lin, Reinhard Falkenstein, Stefan Gries, Hermann Irngartinger

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

AIBN initiated reaction of N-acylaziridines 1 with Bu3SnH in refluxing benzene provided products 5 and 8 of reductive ring opening. Yields (practically quantitative in most cases) fell drastically with steric hindrance of the addition of Bu3Sn. to the acyl oxygen of 1. They depended to some extent on the experimental conditions for hydrogen capturing when aziridine homolysis provided a primary radical 3 or 6. The regioselectivity of (probably reversible) ring homolysis can be understood in terms of the stability of the arising radical (3, 6), of stereoelectronic control (e.g. 1i as compared to 1h) and of frontier orbital interactions (1j). A possible difference in bond lengths as explanation for the formation of the primary radical from 1j did not find support from an X-ray structure analysis of N-tosyl-2-methyl-aziridine 11. Isomeric products were obtained only twice (1i, 1j) with a dependence of the ratio 5j:8j on concentration and hydrogen isotope of Bu3SnH. No such dependence was found for the ratio 5:14 (reduction without and with an intervening cyclization of 3 leading to a pyrrolidone) obtained from the N-cinnamoylaziridine 11. This ratio (1:9 for 11 and 1:3 for 1n) must reflect the E-Z isomers in 3. The observed preference for the formation of E-3 from 2 can be explained by stereoelectronic and steric effects. A cinnamoyl double bond in 5 was saturated depending on experimental conditions.

Original languageEnglish
Pages (from-to)5015-5028
Number of pages14
JournalTetrahedron
Volume45
Issue number16
DOIs
Publication statusPublished - 1989
Externally publishedYes

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Regioselectivity
Hydrogen
Pyrrolidinones
Cyclization
Bond length
Benzene
Isotopes
Isomers
X-Rays
Oxygen
X rays
tributyltin
aziridine
azobis(isobutyronitrile)

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Homolytic aziridine opening (aza variant of cyclopropylcarbinyl-homoallyl rearrangement) by addition of tributyltin radical to N-acylaziridines. Factors contributing to the regioselectivity. / Werrya, Jürgen; Stamm, Helmut; Lin, Pen Yuan; Falkenstein, Reinhard; Gries, Stefan; Irngartinger, Hermann.

In: Tetrahedron, Vol. 45, No. 16, 1989, p. 5015-5028.

Research output: Contribution to journalArticle

Werrya, Jürgen ; Stamm, Helmut ; Lin, Pen Yuan ; Falkenstein, Reinhard ; Gries, Stefan ; Irngartinger, Hermann. / Homolytic aziridine opening (aza variant of cyclopropylcarbinyl-homoallyl rearrangement) by addition of tributyltin radical to N-acylaziridines. Factors contributing to the regioselectivity. In: Tetrahedron. 1989 ; Vol. 45, No. 16. pp. 5015-5028.
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abstract = "AIBN initiated reaction of N-acylaziridines 1 with Bu3SnH in refluxing benzene provided products 5 and 8 of reductive ring opening. Yields (practically quantitative in most cases) fell drastically with steric hindrance of the addition of Bu3Sn. to the acyl oxygen of 1. They depended to some extent on the experimental conditions for hydrogen capturing when aziridine homolysis provided a primary radical 3 or 6. The regioselectivity of (probably reversible) ring homolysis can be understood in terms of the stability of the arising radical (3, 6), of stereoelectronic control (e.g. 1i as compared to 1h) and of frontier orbital interactions (1j). A possible difference in bond lengths as explanation for the formation of the primary radical from 1j did not find support from an X-ray structure analysis of N-tosyl-2-methyl-aziridine 11. Isomeric products were obtained only twice (1i, 1j) with a dependence of the ratio 5j:8j on concentration and hydrogen isotope of Bu3SnH. No such dependence was found for the ratio 5:14 (reduction without and with an intervening cyclization of 3 leading to a pyrrolidone) obtained from the N-cinnamoylaziridine 11. This ratio (1:9 for 11 and 1:3 for 1n) must reflect the E-Z isomers in 3. The observed preference for the formation of E-3 from 2 can be explained by stereoelectronic and steric effects. A cinnamoyl double bond in 5 was saturated depending on experimental conditions.",
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