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-DDQ 2 , tetrahydrobelt[8]arene-TCNE 2 , and belt[8]arene-DDQ 4 adducts. Formation of belt[8]arene, a fully conjugated hydrocarbon belt, was observed from retro-Diels− Alder reaction of a belt[8]arene-DDQ 4 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.

We report in this communication the synthesis, structure, and application of a novel type of hydrocarbon belts. Starting from inexpensive and easily available resorcin[n]arenes, a closing-all-fjords strategy featuring exhaustive triflation of phenolic hydroxyl groups followed by consecutively the transition-metal-catalyzed vinylation and intramolecular olefin metathesis allowed facile construction of belt[n]arene[n]tropilidenes (n = 4, 6), which adopt double-stranded macrocyclic belt structures with unique truncated cone cavities. Selective hydrogenation reactions of olefin and benzene subunits led to diverse hydrocarbon belts with varied structures. Moreover, the resulting molecular belts acted as synthetic host materials to include selectively small molecules such as nitromethane and p-xylene.

We report herein a strategy to construct enantiopure inherently chiral macrocycles, ABCD-type heteracalix[4]aromatics, through a catalytic enantioselective intramolecular C−N bond forming reaction. A chiral ligand-palladium complex was found to efficiently induce the inherent chirality of molecules during the macrocyclization process with ee values up to >99%. The resulting ABCD-type heteracalix[4]aromatics displayed excellent and pH-triggered switchable electronic circular dichroism and circularly polarized luminescence properties.

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