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. 2021 Nov 5;86(21):14956-14963.
doi: 10.1021/acs.joc.1c01679. Epub 2021 Oct 22.

On the Stability and Formation of Pillar[ n]arenes: a DFT Study

Han Zuilhof  1   2   3 , Andrew C-H Sue  4 , Jorge Escorihuela  5
Affiliations

On the Stability and Formation of Pillar[ n]arenes: a DFT Study

Han Zuilhof et al. J Org Chem. .

Abstract

The increased use of both pillar[5]arenes and pillar[6]arenes, stimulated by increasingly efficient syntheses of both, has brought forward the question as to what drives the intermediates in this Friedel-Crafts ring formation to form a pillar[5]arene, a pillar[6]arene, or any other sized macrocycle. This study sets out to answer this question by studying both the thermodynamics and kinetics involved in the absence and presence of templating solvents using high-end wB97XD/6-311G(2p,2d) DFT calculations.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Aim of this study: (a) study of thermodynamics of differently sized pillararenes (n = 4–8); (b) study of kinetics of pillar[5]arene and pillar[6]arene formation, and (c) the role of templating solvents.
Figure 2
Figure 2
Conformations of different sized pillararenes (n = 4–8) and relative stability (E + ZPE) of these pillar[n]arenes per monomer compared to P5 (in kcal/mol). Note: E + ZPE is calculated at the wB97XD/6-311G(2d,2p) level in vacuo and in ACN (in brackets).
Figure 3
Figure 3
Mechanistic steps for ring closure in the formation of pillar[n]arenes (indicated here for P5); departing H and positive charge are given in red for clarity.
Figure 4
Figure 4
Energy diagram (in kcal/mol), in ACN, for the formation of Pns and relevant intermediates relative to their reactants: (A) without template and (B) with DCE in the cavity. Note: water molecules formed are not shown for brevity, but n H2O is taken into account in calculations.
Figure 5
Figure 5
TSs for ring-closure to form protonated P5 (C···C bond-forming distance is given in Å). (A) Nearly C5 symmetric TS; (B) attack from the inside; and (C–F): TS for P5 formation with the solvent in cavity, namely, DCE (C), chlorocyclohexane (D), CHCl3 (E), and CH2Cl2 (F).
Figure 6
Figure 6
TSs for ring closure to form protonated P6 (C···C bond-forming distance is given in Å). (A,B) Different views of TSs for P6 formation; (C–F) TS for P6 formation with the solvent in cavity, namely, DCE (C), chlorocyclohexane (D), CHCl3 (E), and CH2Cl2 (F).
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