Theoretical investigation of enantioselectivity of cage‐like supramolecular assembly: The insights into the shape complementarity and host–guest interaction. Issue 7 (6th January 2015)

• Record Type: Journal Article
• Authors: Ootani, Yusuke; Akinaga, Yoshinobu; Nakajima, Takahito
• Is Part Of: Journal of computational chemistry. Volume 36:Issue 7(2015)
• Page Start: 459
• Page End: 466
• Publication Date: 2015-01-06
• Subjects: Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.23821
• Languages: English
• ISSNs: 0192-8651

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>Enantioselectivity in the aza‐Cope rearrangement of a guest molecule encapsulated in a cage‐like supramolecular assembly [Ga<sub>4</sub>L<sub>6</sub>]<sup>12−</sup> [L = 1, 5‐bis(2', 3'‐dihydroxybenzamido)naphthalene] is investigated using density functional theory and <italic>ab initio</italic> molecular orbital calculations. Reaction pathways leading to <italic>R</italic>‐ and <italic>S</italic>‐enantiomers encapsulated in the [Ga<sub>4</sub>L<sub>6</sub>]<sup>12−</sup> are explored. The reaction barriers and the stabilities of the prochiral structures differed in the [Ga<sub>4</sub>L<sub>6</sub>]<sup>12−</sup>, resulting that the product with an <italic>R</italic> structure is favorably produced in the Δ‐structure [Ga<sub>4</sub>L<sub>6</sub>]<sup>12−</sup>. The large energy difference in the prochiral structures in the [Ga<sub>4</sub>L<sub>6</sub>]<sup>12−</sup> was attributed to the deformation of the bulky substituent. The host–guest interaction energy raises the reaction barrier for the product with an <italic>S</italic> 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. © 2015 Wiley Periodicals, Inc.</p> </abstract>