Dimethyldioxirane Oxidation of 3‐Arylidenechromanones

Waldemar Adam, Judit Halász, A. Lévai, Csaba Nemes, T. Patonay, Gábor Tóth

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Oxidation of the (E) and (Z) isomers of the 3‐arylidenechromanones 5 by isolated dimethyldioxirane (as acetone solution) at ambient temperature resulted in the formation of the spiro epoxides trans‐ and cis‐6, respectively, in moderate yields (23–51%), together with considerable amounts (16–40%) of the 3‐aroylchromones 7 from both (E)‐ and (Z)‐5 isomers. Minor products, namely 3‐(α‐hydroxy‐4‐methoxy‐benzyl)‐4H‐1‐benzopyran‐4‐one (8b), 1a,7a‐dihydro‐7a‐(α‐hydroxy‐4‐methylbenzyl)‐7H‐oxireno[b][1]benzopyran‐7‐one (9d), and the 1a,7a‐dihydro‐7a‐aroyl‐7H‐oxireno[b][1]‐benzopyran‐4‐ones 10a–c have also been isolated and characterized. Presumably, the formation of 3‐aroylchromones 7 can be attributed to competitive allylic oxidation with dimethyldioxirane to afford first the 3‐(α‐hydroxyarylmethyl)‐chromones 8, whose secondary alcohol functionality is subsequently oxidized by dimethyldioxirane to give the 3‐aroylchromones 7. Further oxidation of the latter by dioxirane affords the epoxides 10, as established by a control experiment. Alternatively, first oxidation of 8 to yield epoxide 9 and subsequent oxidation of the alcohol functionality to afford the overoxidized product 10 cannot be disposed of on grounds of our product data. Nonetheless, despite the moderate yields of the desirable chromanone epoxides 6, the stereoselective oxidation directly of the chromanones by dimethyldioxirane offers a convenient preparation. Relative configuration and stereochemistry of compounds 6–10 were elucidated by NMR spectroscopy and AM1 calculations. (Formula Presented.)

Original languageEnglish
Pages (from-to)795-803
Number of pages9
JournalLiebigs Annalen der Chemie
Volume1994
Issue number8
DOIs
Publication statusPublished - 1994

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Epoxy Compounds
Chromones
Alcohols
Acetone
Magnetic Resonance Spectroscopy
Temperature
dimethyldioxirane

Keywords

  • Chromanones
  • Dimethyldioxirane
  • Epoxides

ASJC Scopus subject areas

  • Medicine(all)

Cite this

Dimethyldioxirane Oxidation of 3‐Arylidenechromanones. / Adam, Waldemar; Halász, Judit; Lévai, A.; Nemes, Csaba; Patonay, T.; Tóth, Gábor.

In: Liebigs Annalen der Chemie, Vol. 1994, No. 8, 1994, p. 795-803.

Research output: Contribution to journalArticle

Adam, Waldemar ; Halász, Judit ; Lévai, A. ; Nemes, Csaba ; Patonay, T. ; Tóth, Gábor. / Dimethyldioxirane Oxidation of 3‐Arylidenechromanones. In: Liebigs Annalen der Chemie. 1994 ; Vol. 1994, No. 8. pp. 795-803.
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N2 - Oxidation of the (E) and (Z) isomers of the 3‐arylidenechromanones 5 by isolated dimethyldioxirane (as acetone solution) at ambient temperature resulted in the formation of the spiro epoxides trans‐ and cis‐6, respectively, in moderate yields (23–51%), together with considerable amounts (16–40%) of the 3‐aroylchromones 7 from both (E)‐ and (Z)‐5 isomers. Minor products, namely 3‐(α‐hydroxy‐4‐methoxy‐benzyl)‐4H‐1‐benzopyran‐4‐one (8b), 1a,7a‐dihydro‐7a‐(α‐hydroxy‐4‐methylbenzyl)‐7H‐oxireno[b][1]benzopyran‐7‐one (9d), and the 1a,7a‐dihydro‐7a‐aroyl‐7H‐oxireno[b][1]‐benzopyran‐4‐ones 10a–c have also been isolated and characterized. Presumably, the formation of 3‐aroylchromones 7 can be attributed to competitive allylic oxidation with dimethyldioxirane to afford first the 3‐(α‐hydroxyarylmethyl)‐chromones 8, whose secondary alcohol functionality is subsequently oxidized by dimethyldioxirane to give the 3‐aroylchromones 7. Further oxidation of the latter by dioxirane affords the epoxides 10, as established by a control experiment. Alternatively, first oxidation of 8 to yield epoxide 9 and subsequent oxidation of the alcohol functionality to afford the overoxidized product 10 cannot be disposed of on grounds of our product data. Nonetheless, despite the moderate yields of the desirable chromanone epoxides 6, the stereoselective oxidation directly of the chromanones by dimethyldioxirane offers a convenient preparation. Relative configuration and stereochemistry of compounds 6–10 were elucidated by NMR spectroscopy and AM1 calculations. (Formula Presented.)

AB - Oxidation of the (E) and (Z) isomers of the 3‐arylidenechromanones 5 by isolated dimethyldioxirane (as acetone solution) at ambient temperature resulted in the formation of the spiro epoxides trans‐ and cis‐6, respectively, in moderate yields (23–51%), together with considerable amounts (16–40%) of the 3‐aroylchromones 7 from both (E)‐ and (Z)‐5 isomers. Minor products, namely 3‐(α‐hydroxy‐4‐methoxy‐benzyl)‐4H‐1‐benzopyran‐4‐one (8b), 1a,7a‐dihydro‐7a‐(α‐hydroxy‐4‐methylbenzyl)‐7H‐oxireno[b][1]benzopyran‐7‐one (9d), and the 1a,7a‐dihydro‐7a‐aroyl‐7H‐oxireno[b][1]‐benzopyran‐4‐ones 10a–c have also been isolated and characterized. Presumably, the formation of 3‐aroylchromones 7 can be attributed to competitive allylic oxidation with dimethyldioxirane to afford first the 3‐(α‐hydroxyarylmethyl)‐chromones 8, whose secondary alcohol functionality is subsequently oxidized by dimethyldioxirane to give the 3‐aroylchromones 7. Further oxidation of the latter by dioxirane affords the epoxides 10, as established by a control experiment. Alternatively, first oxidation of 8 to yield epoxide 9 and subsequent oxidation of the alcohol functionality to afford the overoxidized product 10 cannot be disposed of on grounds of our product data. Nonetheless, despite the moderate yields of the desirable chromanone epoxides 6, the stereoselective oxidation directly of the chromanones by dimethyldioxirane offers a convenient preparation. Relative configuration and stereochemistry of compounds 6–10 were elucidated by NMR spectroscopy and AM1 calculations. (Formula Presented.)

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