Inherently chiral cone-calix[4]arenes via a subsequent upper rim ring-closing/opening methodology

José Augusto Berrocal (Corresponding author), Matthew B. Baker, Laura Baldini, Alessandro Casnati, Stefano Di Stefano

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Access to chiral calix[4]arenes can unlock novel supramolecular architectures for enantioselective catalysis and molecular recognition. However, accessibility to these structures has been significantly hindered so far. We report herein the synthesis and characterization of di- and trifunctionalized cone-calix[4]arenes featuring a lactone moiety spanning the distal positions at the upper rim. The lactones force the whole skeleton to assume pinched-cone conformations. The ring-closure is favored by the high conformational flexibility of the calixarene scaffold. The new lactones are remarkably stable in the solid state, while a quick hydrolysis to restore the parent carboxylic acids occurs in solution under acidic/basic conditions. Slow aminolyses of lactones 2-3 yield inherently chiral products featuring three different functionalities at the upper rim, at room temperature. The subsequent ring-closing/opening methodology presented here highlights the versatility of these lactones as powerful synthons for the preparation of a variety of threefold upper rim functionalized, inherently chiral calix[4]arenes fixed in the cone structure.

Original languageEnglish
Pages (from-to)7255-7264
Number of pages10
JournalOrganic & Biomolecular Chemistry
Volume16
Issue number39
DOIs
Publication statusPublished - 10 Oct 2018

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Lactones
closing
rims
Cones
cones
methodology
rings
versatility
musculoskeletal system
carboxylic acids
closures
Calixarenes
catalysis
hydrolysis
flexibility
Molecular recognition
solid state
preparation
Carboxylic Acids
Catalysis

Cite this

Berrocal, José Augusto ; Baker, Matthew B. ; Baldini, Laura ; Casnati, Alessandro ; Di Stefano, Stefano. / Inherently chiral cone-calix[4]arenes via a subsequent upper rim ring-closing/opening methodology. In: Organic & Biomolecular Chemistry. 2018 ; Vol. 16, No. 39. pp. 7255-7264.
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Inherently chiral cone-calix[4]arenes via a subsequent upper rim ring-closing/opening methodology. / Berrocal, José Augusto (Corresponding author); Baker, Matthew B.; Baldini, Laura; Casnati, Alessandro; Di Stefano, Stefano.

In: Organic & Biomolecular Chemistry, Vol. 16, No. 39, 10.10.2018, p. 7255-7264.

Research output: Contribution to journalArticleAcademicpeer-review

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