Résumé

Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.
langue originaleAnglais
journalAngewandte Chemie International Edition
étatAccepté/sous presse - 2 sept. 2019

Empreinte digitale

Boron Compounds
Boron compounds
Boron
Acidity
Lewis Acids
Atoms
Phosphorus
Acids
Lewis Bases
Covalent bonds
Anions
Negative ions
Carbon
Diffraction
Chemical activation
Nuclear magnetic resonance
Derivatives

Citer ceci

@article{52fe88a86a77477a877e2bb0d02fe145,
title = "Pushing the Lewis Acidity Boundaries of Boron Compounds With Non‐Planar Triarylboranes Derived from Triptycenes",
abstract = "Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.",
author = "{Ben Saida}, Ali and Aur{\'e}lien Chardon and Arnaud Osi and Nikolay Tumanov and Johan Wouters and Adjieufack, {Abel Idrice} and Beno{\^i}t Champagne and Guillaume Berionni",
year = "2019",
month = "9",
day = "2",
language = "English",
journal = "Angewandte Chemie International Edition",
issn = "1521-3773",
publisher = "John Wiley and Sons Ltd",

}

TY - JOUR

T1 - Pushing the Lewis Acidity Boundaries of Boron Compounds With Non‐Planar Triarylboranes Derived from Triptycenes

AU - Ben Saida, Ali

AU - Chardon, Aurélien

AU - Osi, Arnaud

AU - Tumanov, Nikolay

AU - Wouters, Johan

AU - Adjieufack, Abel Idrice

AU - Champagne, Benoît

AU - Berionni, Guillaume

PY - 2019/9/2

Y1 - 2019/9/2

N2 - Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.

AB - Bending the planar trigonal boron atom of triphenylborane by connecting its aryl rings with carbon or phosphorus linkers gave access to a series of 9‐boratriptycene derivatives with unprecedented structures and reactivities. NMR and X‐ray diffraction investigations of the Lewis adducts of these non‐planar boron Lewis acids with weak Lewis bases (OPEt 3 , CH 3 CN, EtOAc, Cl – , Br – , I – ) revealed particularly strong covalent bond formation. The first Lewis adduct of a trivalent boron compounds with the Tf 2 N – anion is reported, illustrating the unrivaled Lewis acidity of these pyramidalized boron Lewis acids. Experimental and quantum‐chemical investigations showed that increasing the pyramidalization of the boron atom and using a cationic phosphonium linker resulted in an exceptional enhancement of Lewis acidity, pushing forward the boundaries of the Lewis acidity scale of trivalent boron Lewis acids. Introduction of a phosphorus and a boron atom at each edge of a triptycene framework, allowed to access new bifunctional Lewis acid‐base 9‐phospha‐10‐boratriptycenes featuring promising reactivity for the activation of carbon‐halogen bonds.

M3 - Article

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1521-3773

ER -