A Modular Synthesis of Substituted Cycloparaphenylenes

Daniel Kohrs; Jonathan Becker; Hermann A Wegner

doi:10.1002/chem.202104239

A Modular Synthesis of Substituted Cycloparaphenylenes

Chemistry. 2022 Feb 7;28(8):e202104239. doi: 10.1002/chem.202104239. Epub 2022 Jan 27.

Authors

Daniel Kohrs^{1

2}, Jonathan Becker³, Hermann A Wegner^{1

2}

Affiliations

¹ Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392, Giessen, Germany.
² Center for Materials Research (ZfM/LaMa), Justus Liebig University Giessen, Heinrich-Buff-Ring 16, 35392, Giessen, Germany.
³ Institute of Inorganic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392, Giessen, Germany.

Abstract

Herein, we report a modular synthesis providing access to substituted cycloparaphenylenes (CPPs) of different sizes. A key synthon introducing two geminal ester units was efficiently prepared by [2+2+2] cycloaddition. This building block can be conveniently converted to macrocyclic precursors controlling the ring size of the final CPP. Efficient reductive aromatization through single-electron transfer provided the substituted nanohoops in a straightforward manner. The tBu ester substitution pattern enables a tube-like arrangement in the solid-state governed by van der Waals interactions that exhibits one of the tightest packings of CPPs in tube direction, thus opening new avenues in the crystal design of CPPs.

Keywords: [2+2+2] cycloaddition; carbon allotropes; cross-coupling; macrocycles; solid-state structures.

MeSH terms

Cycloaddition Reaction*