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. The formation of ternary complexes with acrylonitrile (AN) and 2@β-CD or 3@β-CD was also essayed by ¹H NMR. Although the 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.

中文翻译：

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[3 + 2] 与 β-环糊精中的光生偶氮甲碱叶立德进行环加成。


通过¹ H NMR 滴定测定环己基邻苯二甲酰亚胺2和金刚烷基邻苯二甲酰亚胺3与 β-环糊精 (β-CD) 包合物的稳定性常数，分别为K = 190 ± 50 M ^-1和K = 2600 ± 600 M ^-1 。研究了包合物2@β-CD和3@β-CD的光化学反应活性，发现β-CD不影响脱羧效率，但影响后续光化学H-抽象，导致产物分布不同在 β-CD 存在下进行照射。还通过¹ H NMR 分析了丙烯腈 (AN) 和2@β-CD或3@β-CD的三元配合物的形成。尽管建议形成此类复合物，但无法确定稳定性常数。在 AN 存在的水溶液中照射2@β-CD，形成环加合物7 ，这高度表明三元复合物中发生脱羧和 [3 + 2] 环加成，而大金刚烷3发生这种反应的可能性较小。脱羧和环加成可以在 β-CD 腔中进行的原理证明对于设计用于控制光反应性的新型超分子系统具有重要意义。