The Role of Weak Interactions in Supramolecular Compounds: A Synthetic and Theoretical Study of Novel Elongated Cavitands

Abstract

A new resorcinol-based tetraazidocavitand (2) has been prepared via substitution reaction started from the corresponding tetrabromocavitand (1). This tetraazidocavitand was used as a starting material for azide-alkyne cycloaddition with different alkynes and this way four novel deepened cavitands have been synthesized under mild conditions. Molecular dynamics, semiempirical PM6 and DFT PBEPBE/6-31G(d,p) studies have been carried out for these new triazole ring containing structures to reveal the exact geometry in solution, furthermore theoretical NMR chemical shift calculations were completed at B3LYPÀD3/6-31G(d,p) GIAO level in order to compare with the experimental NMR data. QTAIM analysis at B3LYPÀD3/def2-TZVP level was performed and NCI isosurfaces were generated to reveal the potential intramolecular weak interactions between the cavitand branches.

Mechanism and origin of the stereoselectivity of manganese-catalyzed hydrosilylation of alkynes: a DFT study

“…PBEPBE density functional is one of the "fastest" and most costeffective calculation methods to give the exact geometry. [33][34][35] After the D3 dispersion correction, the enthalpy calculations significantly improve with the G2MP2 ab initio method. 34,35 The geometries of all of the reactants, catalysts, intermediates, transition states, and products were fully optimized at the PBEPBE-D3/def2SVP 36,37 level.…”

27 Years of Catalytic Carbonylative Coupling Reactions in Hungary (1994–2021)

“…Moreover, carbonylative syntheses applied on a cavitand skeletons were not mentioned in the literature at all, with the exception of the works of our research group. In the recent ten years, our research group had developed several palladium-and copper-catalyzed reactions on a cavitand sceleton [86][87][88][89], including palladium-catalyzed aminocarbonylation [90][91][92][93].…”

Synthesis of Novel Cavitand Host Molecules via Palladium-Catalyzed Aryloxy- and Azidocarbonylation

“…In the last decade, our research group had developed and described several palladium- and copper-catalyzed homogeneous catalytic processes on a cavitand scaffold, including the palladium-catalyzed aminocarbonylation [ 13 ], copper-catalyzed azide-alkyne cycloaddition (CuAAC) [ 14 , 15 ] and Sonogashira or Suzuki-Miyaura coupling [ 16 ]. It has been proven that homogeneous catalytic processes can be easily adopted for cavitands, and similar results can be expected in terms of both reactivity and selectivity as in the case of small molecules.…”

“…Primary carboxamides as stable final products were obtained using this protocol. Continuing our investigations on the synthesis of functionalized cavitands [ 13 , 15 , 16 , 35 ], with the aim of their application in host-guest chemistry, homogeneous catalytic reactions were applied for the introduction of novel functionalities. The synthetic strategy of these supramolecular entities is based on the combination of high-yielding conventional procedures and highly selective homogeneous catalytic reactions.…”