Reactivity and Steric Parameters from 2D to 3D Bulky Pyridines: Increasing Steric Demand at Nitrogen with Chiral Azatriptycenes

Author:

Saida Ali Ben1,Mahaut Damien1,Tumanov Nikolay1,Wouters Johan1,Champagne Benoît1,Vanthuyne Nicolas2,Robiette Raphaël3,Berionni Guillaume1ORCID

Affiliation:

1. Department of Chemistry and Namur Institute of Structured Matter Université de Namur 61 Rue de Bruxelles 5000 Namur Belgium

2. Aix Marseille Univ, CNRS, Centrale Marseille, iSm2 Marseille France

3. Institute of Condensed Matter and Nanosciences Université catholique de Louvain Place Louis Pasteur 1 Box L4.01.02 1348 Louvain-la-Neuve Belgium

Abstract

AbstractSterically hindered pyridines embedded in a three‐dimensional triptycene framework have been synthesized, and their resolution by chiral HPLC enabled access to unprecedented enantiopure pyridines exceeding the known steric limits. The design principles for new axially chiral pyridine derivatives are then described. To rationalize their associations with Lewis acids and transition metals, a comprehensive determination of the steric and electronic parameters for this new class of pyridines was performed. This led to the general parameterization of the steric parameters (percent buried volume %VBur, Tolman cone angle θ, and He8_steric descriptor) for a large set of two‐ and three‐dimensional pyridine derivatives. These parameters are shown to describe quantitatively their interactions with carbon‐ and boron‐centered Lewis acids and were used to predict the ΔG° of association with the prototypical B(C6F5)3 Lewis acid widely used in frustrated Lewis pair catalysis. This first parameterization of pyridine sterics is a fundamental basis for the future development of predictive reactivity models and for guiding new applications of bulky and chiral pyridines in organocatalysis, frustrated Lewis pairs, and transition‐metal catalysis.

Funder

HORIZON EUROPE European Research Council

Fonds pour la Formation à la Recherche dans l’Industrie et dans l’Agriculture

Fonds De La Recherche Scientifique - FNRS

Gouvernement Wallon

Publisher

Wiley

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