Theoretical investigation of enantioselectivity of cage-like supramolecular assembly the insights into the shape complementarity and host-guest interaction

Theoretical investigation of enantioselectivity of cage-like supramolecular assembly : the insights into the shape complementarity and host-guest interaction

© 2015 Wiley Periodicals, Inc.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 36(2015), 7 vom: 15. März, Seite 459-66
1. Verfasser: Ootani, Yusuke (VerfasserIn)
Weitere Verfasser: Akinaga, Yoshinobu, Nakajima, Takahito
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2015
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article QM/MM DFT calculation aza-Cope rearrangement host-guest interaction minimum energy path shape complementarity supramolecular chemistry
Beschreibung
Zusammenfassung:© 2015 Wiley Periodicals, Inc.
Enantioselectivity in the aza-Cope rearrangement of a guest molecule encapsulated in a cage-like supramolecular assembly [Ga4 L6 ](12-) [L = 1,5-bis(2',3'-dihydroxybenzamido)naphthalene] is investigated using density functional theory and ab initio molecular orbital calculations. Reaction pathways leading to R- and S-enantiomers encapsulated in the [Ga4 L6 ](12-) are explored. The reaction barriers and the stabilities of the prochiral structures differed in the [Ga4 L6 ](12-) , resulting that the product with an R structure is favorably produced in the Δ-structure [Ga4 L6 ](12-) . The large energy difference in the prochiral structures in the [Ga4 L6 ](12-) was attributed to the deformation of the bulky substituent. The host-guest interaction energy raises the reaction barrier for the product with an S structure. The previous study suggested that the different stability of the prochiral substrates in the assembly was the origin of the enantioselectivity, and the suggestion is supported by our computational finding. In addition, our results show that the difference in the reaction barriers also importantly contributes to the enantioselectivity
Beschreibung:Date Completed 21.05.2015
Date Revised 18.02.2015
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1096-987X
DOI:10.1002/jcc.23821