American Chemical Society
Browse
ja0c00112_si_014.cif (4.59 MB)

Toward the Synthesis of a Highly Strained Hydrocarbon Belt

Download (4.59 MB)
dataset
posted on 2020-02-25, 21:45 authored by Tan-Hao Shi, Qing-Hui Guo, Shuo Tong, Mei-Xiang Wang
Hydrocarbon belts including fully conjugated beltarenes and their (partially) saturated analogs have fascinated chemists for decades due to their aesthetic structures, tantalizing properties, and potential applications in supramolecular chemistry and carbon nanoscience and nanotechnology. However, synthesis of hydrocarbon belts still remains a formidable challenge. We report in this communication a general approach to hydrocarbon belts and their derivatives. Closing up all four fjords of resorcin[4]­arene derivatives through multiple intramolecular Friedel–Crafts alkylation reactions in an operationally simple one-pot reaction manner enabled efficient construction of octohydrobelt[8]­arenes. Synthesis of belt[8]­arene from DDQ-oxidized aromatization of octohydrobelt[8]­arene under different conditions resulted in aromatization and simultaneous [4 + 2] cycloaddition reactions with DDQ or TCNE to produce selectively tetrahydrobelt[8]­arene-DDQ2, tetrahydrobelt[8]­arene-TCNE2, and belt[8]­arene-DDQ4 adducts. Formation of belt[8]­arene, a fully conjugated hydrocarbon belt, was observed from retro-Diels–Alder reaction of a belt[8]­arene-DDQ4 adduct with laser irradiation under MALDI conditions. The new and practical synthetic method established would open an avenue to create belt-shaped molecules from easily available starting materials.

History