Résumé
The stereospecific trimerization of enantiomerically pure binaphthols with hexakis(bromomethyl)benzene gives access in one step to enantiomerically pure molecular propellers, in which three binaphthyl rings are held together with dioxecine rings. X-ray diffraction analysis revealed that three out the six naphthyl moieties are folded in a (EF)3 -type arrangement held by three intramolecular C-H⋅⋅⋅π interactions. This slips outward the three remaining naphthyl rings in a blade-like fashion, just like in three-folded propeller components. This peculiar conformation shows striking similarity to the mythological Sicilian symbol of Trinacria, from which the name "trinacria propeller" derives. The propeller conformation is also preserved in chlorinated solutions, as displayed by the presence of a peak at 4.7 ppm typical of an aromatic proton resonance engaged in a C-H⋅⋅⋅π interaction. The denaturation of the propeller-like conformation is obtained at high temperature, corresponding to activation energy for the ring inversion of ca. 18.2 kcal mol-1 . Notably, halide-functionalized molecular propellers exposing I-atoms at the leading and trailing edges could be prepared stereo- and regiospecifically by choosing the relevant iodo-bearing BINOL derivative.
langue originale | Anglais |
---|---|
Pages (de - à) | 15348-15354 |
Nombre de pages | 7 |
journal | Chemistry - A European Journal |
Volume | 23 |
Numéro de publication | 61 |
Les DOIs | |
Etat de la publication | Publié - 2 nov. 2017 |
Modification externe | Oui |
Empreinte digitale
Examiner les sujets de recherche de « Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers ». Ensemble, ils forment une empreinte digitale unique.Équipement
-
Physico-chimie et caractérisation (PC2)
Johan Wouters (!!Manager) & Carmela Aprile (!!Manager)
Plateforme technologique Caracterisation physico-chimiquesEquipement/installations: Plateforme technolgique
Ensembles de données
-
CCDC 1037157: Experimental Crystal Structure Determination
BONIFAZI, D. (Contributeur), Demitri, N. (Contributeur), Mosca, D. (Contributeur), Stopin, A. (Contributeur) & Wouters, J. (Contributeur), Cambridge Crystallographic Data Centre, 1 janv. 2017
DOI: 10.5517/ccdc.csd.cc13t7pv, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13t7pv&sid=DataCite
Ensemble de données
-
CCDC 1548318: Experimental Crystal Structure Determination
BONIFAZI, D. (Contributeur), Demitri, N. (Contributeur), Mosca, D. (Contributeur), Stopin, A. (Contributeur) & Wouters, J. (Contributeur), Cambridge Crystallographic Data Centre, 1 janv. 2017
DOI: 10.5517/ccdc.csd.cc1nz4rj, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nz4rj&sid=DataCite
Ensemble de données
-
CCDC 1037158: Experimental Crystal Structure Determination
BONIFAZI, D. (Contributeur), Demitri, N. (Contributeur), Mosca, D. (Contributeur), Stopin, A. (Contributeur) & Wouters, J. (Contributeur), Cambridge Crystallographic Data Centre, 1 janv. 2017
DOI: 10.5517/ccdc.csd.cc13t7qw, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13t7qw&sid=DataCite
Ensemble de données