ja0c00112_si_014.cif (4.59 MB)
Toward the Synthesis of a Highly Strained Hydrocarbon Belt
dataset
posted on 2020-02-25, 21:45 authored by Tan-Hao Shi, Qing-Hui Guo, Shuo Tong, Mei-Xiang WangHydrocarbon 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.