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An intramolecularly self-templated synthesis of macrocycles: self-filling effects on the formation of prismarenes.

Authors :
Della Sala P
Del Regno R
Di Marino L
Calabrese C
Palo C
Talotta C
Geremia S
Hickey N
Capobianco A
Neri P
Gaeta C
Source :
Chemical science [Chem Sci] 2021 Jun 03; Vol. 12 (29), pp. 9952-9961. Date of Electronic Publication: 2021 Jun 03 (Print Publication: 2021).
Publication Year :
2021

Abstract

Ethyl- and propyl-prism[6]arenes are obtained in high yields and in short reaction times, independent of the nature and size of the solvent, in the cyclization of 2,6-dialkoxynaphthalene with paraformaldehyde. PrS[6]Et or PrS[6]nPr adopt, both in solution and in the solid state, a folded cuboid-shaped conformation, in which four inward oriented alkyl chains fill the cavity of the macrocycle. On these bases, we proposed that the cyclization of PrS[6]Et or PrS[6]nPr occurs through an intramolecular thermodynamic self-templating effect. In other words, the self-filling of the internal cavity of PrS[6]Et or PrS[6]nPr stabilizes their cuboid structure, driving the equilibrium toward their formation. Molecular recognition studies, both in solution and in the solid state, show that the introduction of guests into the macrocycle cavity forces the cuboid scaffold to open, through an induced-fit mechanism. An analogous conformational change from a closed to an open state occurs during the endo -cavity complexation process of the pentamer, PrS[5] . These results represent a rare example of a thermodynamically controlled cyclization process driven through an intramolecular self-template effect, which could be exploited in the synthesis of novel macrocycles.<br />Competing Interests: There are no conflicts to declare.<br /> (This journal is © The Royal Society of Chemistry.)

Details

Language :
English
ISSN :
2041-6520
Volume :
12
Issue :
29
Database :
MEDLINE
Journal :
Chemical science
Publication Type :
Academic Journal
Accession number :
34349965
Full Text :
https://doi.org/10.1039/d1sc02199k