By exploiting the supramolecular assistance of a sterically encumbered phenanthroline-Cu(+) motif, we report on the self-assembly of a trigonal nanoprism, its post-self-assembly functionalization, and transformation into a cage-like 3D framework with distinct compartments.
Herein, we present the Pd(II)-catalyzed atroposelective C–H acyloxylation strategy for the assembly of biaryl aldehyde atropoisomers using readily available amino acids as the catalytic auxiliary and chiral pool. This strategy exhibits a broad substrate scope with a good yield (≤90%) and excellent enantioselectivity (≤99%), furnishing functionalized aldehydes through direct asymmetric C–H oxidation. The application utility of this method was demonstrated by the concise synthesis of a kind of atropoisomeric amino-phenol organocatalyst, which enables good enantiocontrol in catalyzing asymmetric addition of diethylzinc to aldehydes.
A metallosupramolecular prismatic nanocage with altogether six reactive aldehyde terminals was utilized as a sophisticated "monomer" in a template-directed constitutional dynamic imine polymerization to prepare an unprecedented triple-stranded dynamer. To analyze the correlated growth in its three congener strands, a fully covalent triple-armed star polymer was fabricated from the metallodynamer through capping, imine reduction, and removal of the template. Atomic force microscopy analysis of 68 triple-armed star polymer molecules suggests that the growth of their arms is correlated to ∼72%.
The quantitative preparation of heteroleptic copper(I) complexes arising from a combination of 2,9-diarylphenanthrolines and iminopyridines (Schiff bases) is described. This strategy was applied to construct mono- and binuclear complexes but equally a discrete three-dimensional M(3)LL' cage. By means of a constitutional dynamic synthesis, the heteroleptic aggregates were equally prepared from four-component mixtures using the copper(I) center as a catalyst for the in situ generation of the iminopyridine ligands.
A copper-mediated tandem addition/cyclization/carbon–carbon cleavage reaction for the convenient synthesis of 2-acyl trisubstituted furans has been developed.
The tetrahedral [Cu(phenAr2)(py)2]+ coordination motif (phen = 1,10-phenanthroline; py = pyridine) conceived on the basis of the HETPYP concept (heteroleptic pyridyl and phenanthroline metal complexes) is a versatile dynamic unit for constructing various heteroleptic metallosupramolecular pseudo-1D, 2D, and 3D structures, both in solution and the solid state. The 2,9-diaryl substituted phenanthroline (phenAr2) serves as a capping ligand for copper(I) ions, as its bulky nature prevents formation of the homoleptic complex [Cu(phenAr2)2]+. Combination of the dynamic and concave metal ligand building block [Cu(phenAr2)]+ with various pyridine (py) ligands, such as bi-, tri-, and tetra-pyridines, opened the way to infinite 1D helicates, 2D networks, and discrete 3D hexanuclear cages, whereas spatial integration of both phenAr2 and py units into a single ligand resulted in the formation of a Borromean-ring-type hexanuclear cage.
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