Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers

Résultats de recherche: Contribution à un journal/une revueArticle

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 originaleAnglais
Pages (de - à)15348-15354
Nombre de pages7
journalChemistry - A European Journal
Volume23
Numéro de publication61
Les DOIs
étatPublié - 2 nov. 2017
Modification externeOui

Empreinte digitale

Polycyclic Aromatic Hydrocarbons
Propellers
Polycyclic aromatic hydrocarbons
Conformations
Bearings (structural)
Denaturation
Benzene
X ray diffraction analysis
Protons
Activation energy
Derivatives
Atoms
Hydrogen

Citer ceci

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abstract = "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.",
keywords = "Journal Article, molecular propellers, chirality, aromatic embrace, molecular motors, polycycles",
author = "Dario Mosca and Antoine Stopin and Johan Wouters and Nicola Demitri and Davide Bonifazi",
note = "{\circledC} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",
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Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers. / Mosca, Dario; Stopin, Antoine; Wouters, Johan; Demitri, Nicola; Bonifazi, Davide.

Dans: Chemistry - A European Journal, Vol 23, Numéro 61, 02.11.2017, p. 15348-15354.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers

AU - Mosca, Dario

AU - Stopin, Antoine

AU - Wouters, Johan

AU - Demitri, Nicola

AU - Bonifazi, Davide

N1 - © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2017/11/2

Y1 - 2017/11/2

N2 - 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.

AB - 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.

KW - Journal Article

KW - molecular propellers

KW - chirality

KW - aromatic embrace

KW - molecular motors

KW - polycycles

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DO - 10.1002/chem.201702032

M3 - Article

VL - 23

SP - 15348

EP - 15354

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 61

ER -