ABSTRACT
O6-Corona[3]arene[3]tetrazines with expanded cavities were synthesized by one-pot SNAr reaction between 3,6-dichlorotetrazine and aromatic diols. The macrocycle-to-macrocycle transformation involving IEDDA of tetrazine moieties with an enamine followed by denitrogenative aromatization afforded O6-corona[3]arene[3]pyridazines. O6-Corona[6]arenes adopted coronary conformations yielding hexagonal cavities of varied sizes. While O6-corona[3]arene[3]pyridazines complexed both C60 and C70 in a virtually nonselective manner, O6-corona[3]arene[3]tetrazines behaved as selective receptors to complex C70 with K1:1 values up to (3.98 ± 0.08) × 104 M-1 in toluene.
ABSTRACT
A one-pot nucleophilic aromatic substitution reaction of 3,6-dichlorotetrazine with various diphenols and dibenzenethiols produced corona[4]arene[2]tetrazines that contain mixed oxygen, sulfide, methylene, and sulfone linkages. Macrocyclic ring transformations employing an inverse-electron-demand Diels-Alder reaction of tetrazine moieties with enamines and the subsequent sulfide oxidation reaction afforded diverse corona[4]arene[2]pyridazines. The acquired corona[6]arenes adopted three types of conformational structures in the crystalline state.
ABSTRACT
O6 -Corona[3]arene[3]tetraazines, a new class of macrocyclic compounds, were synthesized efficiently in a one-pot reaction from the nucleophilic aromatic substitution reaction between 1,4-dihydroxybenzene derivatives and 3,6-dichlorotetrazine in warm acetonitrile. In the crystalline structure, the resulting macrocycles adopt highly symmetric structures of a regular hexagonal cavity with all bridging oxygen atoms and tetrazine rings located on the same plane with phenylene units orthogonally orientated. The constitutional aromatic rings are able to rotate around the macrocyclic annulus, depending on the steric effect of the substituents and temperature, in solution. The electron-deficient nature revealed by cyclic voltammetry, differential pulse voltammetry, and characteristic absorbances at a visible region show the O6 -corona[3]arene[3]tetrazines to be suitable macrocyclic receptors for electron-rich guests.
