[3+2] cycloaddition with photogenerated azomethine ylides in β-cyclodextrin

Margareta, Sohora; Mandić, Leo; Basarić, Nikola (2020) [3+2] cycloaddition with photogenerated azomethine ylides in β-cyclodextrin. Beilstein Journal of Organic Chemistry, 16 . pp. 1296-1304. ISSN 1860-5397

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Abstract

Stability constants for the inclusion complexes of cyclohexylphthalimide 2 and adamantylphthalimide 3 with β-cyclodextrin (β-CD) were determined by 1H NMR titration, K = 190 ± 50 M-1, and K = 2600 ± 600 M-1, respectively. Photochemical reactivity of the inclusion complexes 2@β-CD and 3@β-CD was investigated, and we found out that β-CD does not affect the decarboxylation efficiency, while it affects the subsequent photochemical H-abstraction, resulting in different product distribution upon irradiation in the presence of β-CD. Formation of ternary complexes with acrylonitrile (AN) and 2@β-CD or 3@β-CD was also essayed by 1H NMR. Although formation of such complexes was suggested, stability constants could not be determined. Irradiation of 2@β-CD in the presence of AN in aqueous solution where cycloadduct 7 was formed highly suggests that decarboxylation and [3+2] cycloaddition take place in the ternary complex, whereas such a reactivity from bulky adamantane 3 is less likely. This proof of principle that decarboxylation and cycloaddition can be performed in the β-CD cavity has a significant importance for the design of new supramolecular systems for the control of photoreactivity.

Item Type:

Article

Uncontrolled Keywords:

[3 + 2] cycloadditions ; β-cyclodextrin ; inclusion complexes ; photochemistry ; phthalimides

Subjects:

NATURAL SCIENCES > Chemistry

Divisions:

Division of Materials Chemistry
Division of Organic Chemistry and Biochemistry

Projects: