期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 88, 期 19, 页码 13655-13665出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.3c01343
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This study provides important insights into the theoretical analysis of complex molecular reactions by investigating the conformations and stereoselectivity of transition states. The findings reveal that the double-bond geometry and stereochemical configuration influence the conformations of the transition states, and that the CH-O hydrogen bond and CH-p interaction play critical roles in asymmetric induction.
An accurate understanding of conformations in transition states is a critical piece in the theoretical analysis of complex molecular reactions. In this study, we investigated conformationally diverse transition states during intramolecular aza-spiro ring formation with an allylsilane moiety and N-alkoxy iminium ion, a key reaction in the synthesis of fasicularin by Sato and Chida et al., and identified the origins of stereoselectivity of the cyclization. A large number of conformational isomers with forming C-C bonds were comprehensively analyzed using Cremer-Pople puckering parameters. It was found that the conformations of the transition states had different puckering preferences depending on the reactant's double-bond geometry and the product's stereochemical configuration. Furthermore, an asymmetric aza-spiro cyclization with a tolyl group as a chiral auxiliary was investigated, showing that conformational anchoring by both a CH-O hydrogen bond and the CH-p interaction was critical for the asymmetric induction.
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