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Stereochemical Stability of Planar-Chiral Benzazepine Tricyclics: Inversion Energies of P- and S-Alkene Ligands


Calderón, Jacqueline C; Herrera, Alberto; Heinemann, Frank W; Langer, Jens; Linden, Anthony; Chelouan, Ahmed; Grasruck, Alexander; Añez, Rafael; Clark, Timothy; Dorta, Romano (2023). Stereochemical Stability of Planar-Chiral Benzazepine Tricyclics: Inversion Energies of P- and S-Alkene Ligands. Journal of Organic Chemistry, 88(23):16144-16154.

Abstract

Inversion barriers ΔG‡ for planar chiral phosphine-alkene and sulfonamide-alkene hybrid ligands based on phenyl-dibenz[b,f]azepine have been determined by density-functional theory calculations. Analysis of the structural and electronic characteristics of the minima and transition states explains the magnitudes of ΔG‡ and the geometrical changes during the inversion process. The steric repulsion caused by bulky substituents attached to the azepine nitrogen atom has a pronounced effect on the ΔG‡ value, explaining, inter alia, the stereochemical stability of the P- and S-alkene ligands when compared to the fluxional parent compound where X = H.

Abstract

Inversion barriers ΔG‡ for planar chiral phosphine-alkene and sulfonamide-alkene hybrid ligands based on phenyl-dibenz[b,f]azepine have been determined by density-functional theory calculations. Analysis of the structural and electronic characteristics of the minima and transition states explains the magnitudes of ΔG‡ and the geometrical changes during the inversion process. The steric repulsion caused by bulky substituents attached to the azepine nitrogen atom has a pronounced effect on the ΔG‡ value, explaining, inter alia, the stereochemical stability of the P- and S-alkene ligands when compared to the fluxional parent compound where X = H.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Organic Chemistry
Uncontrolled Keywords:Organic Chemistry
Language:English
Date:1 December 2023
Deposited On:05 Jan 2024 08:48
Last Modified:30 Jun 2024 01:36
Publisher:American Chemical Society (ACS)
ISSN:0022-3263
Additional Information:I have uploaded the published version. Despite my request to Prof Dorta, I do not have a copy of the final revised version submitted to the journal. Please approach the correspondence authors if you wish to try to obtain the final submitted version.
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.joc.3c01447
PubMed ID:37944159
Project Information:
  • : FunderFriedrich-Alexander-Universit?t Erlangen-N?rnberg
  • : Grant ID
  • : Project Title