Triple Thorpe-Ingold Effect in the Synthesis of 18-Membered C Symmetric Lactams Stacking as Endless Supramolecular Tubes.

Three C symmetric macrolactams were very efficiently cyclized from their linear precursors. Adequately located substituents are responsible for the enhancement of reactivity that is not observed in the unsubstituted parent. DFT calculations show that the properly folded cyclization precursor, the reactive conformer, is more populated than other conformers, leading to a decrease of free energy of activation.

Single-Electron Transfer from Dimsyl Anion in the Alkylation of Phenols.

While attempting to synthesize biaryl ethers we discovered the inadvertent formation of a methylsulfoxylmethyl ether byproduct. Formation of this unexpected byproduct presented an opportunity to streamline the synthesis of methylsulfoxylmethyl ethers. Mechanistic studies suggest a radical pathway with dimsyl potassium as a reducing agent.

Self-Assembly of C Symmetric Rigid Macrolactams into Very Polar and Porous Trigonal Crystals.

Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C -symmetric rings incorporating conjugated alkenes and dienes. All three C -symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively.

Diffusion of chiral molecules and propagation of structural chirality in anisotropic liquids.

Diffusion in nature is usually considered as a smooth redistribution process. However, it appears that the diffusion of chiral molecules and the propagation of chirality may proceed in quite different ways. Indeed, in the present work, unexpected quantization of the spatial concentration of chiral molecules is discovered in self-aligned molecular liquids.