Toward Strained Pillar[4]arene Derivatives

Ke Liu; Zhe Liu; Xue Chen; Yang Liu; Qing-Hui Guo

doi:10.1055/a-2627-8429

Synlett, Table of Contents

Synlett
DOI: 10.1055/a-2627-8429

Letter

Toward Strained Pillar[4]arene Derivatives

Ke Liu

¹Department of Chemistry, Stoddart Institute of Molecular Science, Zhejiang University, Hangzhou, China

²Department of Chemistry, MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Tsinghua University, Beijing, China

,

Zhe Liu

¹Department of Chemistry, Stoddart Institute of Molecular Science, Zhejiang University, Hangzhou, China

,

Xue Chen

¹Department of Chemistry, Stoddart Institute of Molecular Science, Zhejiang University, Hangzhou, China

²Department of Chemistry, MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Tsinghua University, Beijing, China

,

Yang Liu

¹Department of Chemistry, Stoddart Institute of Molecular Science, Zhejiang University, Hangzhou, China

²Department of Chemistry, MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Tsinghua University, Beijing, China

,

Qing-Hui Guo

¹Department of Chemistry, Stoddart Institute of Molecular Science, Zhejiang University, Hangzhou, China

²Department of Chemistry, MOE Key Laboratory of Bioorganic Phosphorous and Chemical Biology, Tsinghua University, Beijing, China

› Author Affiliations

Abstract

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Abstract

Over the past decade, pillar[n]arenes have emerged as prominent macrocyclic hosts in supramolecular chemistry owing to their straightforward synthesis, versatile functionalization, and rigid columnar cavities, attracting considerable research interest. However, conventional Lewis acid-catalyzed cyclizations exhibit an inherent preference for larger pillar[n]arenes (n ≥ 5) due to kinetic and thermodynamic factors associated with the dynamic oligomerization process, thereby precluding the synthesis of strained pillar[4]arene architectures. To overcome this challenge, we developed an innovative strain-engineering strategy—from low to high strain—based on a key thiophene-to-benzene transformation. This approach involves stepwise thiophene oxidation followed by an inverse electron-demand Diels–Alder (IEDDA) reaction, dynamically driven by SO₂ extrusion. High-resolution mass spectrometry confirmed the formation of tetrahydro-pillar[4]arene derivatives in the reaction mixture through their characteristic isotopic patterns. Our work establishes a viable route to challenging, strained pillar[4]arenes.

Keywords

Pillar[4]arene - Strained macrocyclic arenes - Dynamic-driven transformation - Inverse electron-demand Diels–Alder reaction

Full Text

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Supplementary Material

Supplementary Material