Reaction of isonitriles with 3-(arylamino)isobenzofuran-1(3H)-ones in the presence of a catalytic amount of an octahydro (R)-binol-derived chiral phosphoric acid afforded 3-oxo-2-arylisoindoline-1-carboxamides in high yields with good to high enantioselectivities. An enantioselective Ugi four-center three-component reaction of 2-formylbenzoic acids, anilines, and isonitriles was subsequently developed for the synthesis of the same heterocycle. Mechanistic studies indicate that the enantioselectivity results from the dynamic kinetic resolution of the primary Ugi adduct, rather than from the C−C bond-forming process. The resulting heterocycle products are of significant medicinal importance.

Reaction of isonitriles with 3-(arylamino)isobenzofuran-1(3H)-ones in the presence of a catalytic amount of an octahydro (R)-binol-derived chiral phosphoric acid afforded 3-oxo-2-arylisoindoline-1-carboxamides in high yields with good to high enantioselectivities. An enantioselective Ugi four-center three-component reaction of 2-formylbenzoic acids, anilines, and isonitriles was subsequently developed for the synthesis of the same heterocycle. Mechanistic studies indicate that the enantioselectivity results from the dynamic kinetic resolution of the primary Ugi adduct, rather than from the C−C bond-forming process. The resulting heterocycle products are of significant medicinal importance.

Anion–π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self-assembly induced by anion–π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion–π interactions, and the subsequent formation of self-assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host–guest supramolecular amphiphiles and self-assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion–π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO₃⁻, Cl⁻, and Br⁻, or by changing the pH value of the medium.

Anion–π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self-assembly induced by anion–π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion–π interactions, and the subsequent formation of self-assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host–guest supramolecular amphiphiles and self-assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion–π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO₃⁻, Cl⁻, and Br⁻, or by changing the pH value of the medium.

A number of azacalix[2]pyrimidine[2]triazines were synthesized in moderate to good yields from both a step-wise fragment coupling approach and a one-pot reaction strategy starting from 4,6-diaminopyrimidines and cyanuric chloride. Nucleophilic aromatic substitution reaction of resulting dichloro-substituted azacalix[2]pyrimidine[2]triazines with NH₄Cl led to the formation of NH₂-bearing azacalix[2]pyrimidine[2]triazine analogs. Azacalix[2]pyrimidine[2]triazines adopted symmetric 1,3-alternate conformations in solution while twisted 1,3-alternate conformations were observed in the solid state. In the presence of different additives during the growth of single crystals, azacalix[2]pyrimidine[2]triazines containing amino (-NH₂) groups gave varied self-assembled structures due to the formation of different intermolecular hydrogen bond motifs.

Taking tetraoxacalix[2]arene[2]triazine as a functionalization platform, a series of new amphiphilic molecules were synthesized in 18 to 53 % yields by using a fragment coupling protocol. These amphiphilic molecules self-assembled into stable vesicles in a mixture of THF and water, with the surface of the vesicles engineered by electron-deficient cavities. Various anions are able to selectively influence the size of self-assembled vesicles, following the order of F⁻<ClO₄⁻<SCN⁻<BF₄⁻<Br⁻<Cl⁻<NO₃⁻, as revealed by DLS measurements. Such a sequence was independent with the hydration cost and in agreement with the binding strength of anions with tetraoxacalix[2]arene[2]triazine host molecule, indicating that the anion–π interaction most probably competed over other possible weak interactions and accounted for this interesting selectivity. In addition, the chloride permeation process across the membrane of the vesicles was also preliminarily studied by means of fluorescent experiments. This study, in addition to providing the potentiality of heteracalixaromatics as new models to construct functional vesicles, opens a new avenue to study the anion–π interactions in aqueous and also potentially in living systems.

Disulfane-linked bisazacalix[n]pyridines (n=4, 7) were synthesized for the first time using a macrocyclic fragment coupling approach followed by post-macrocyclization photoreaction with ethanethioic acid and hydrolysis under basic conditions. The bis-macrocyclic compounds acted as strong receptors to form 1:1 complex with C₆₀ and C₇₀, giving a binding constant (K_a(1:1)) up to 107000 L·mol⁻¹. The cooperation of two mono-macrocyclic improved binding affinity to fullerenes.