Hierarchically assembled helicates as reaction platform - from stoichiometric Diels-Alder reactions to enamine catalysis.

The stereoselectivity of a Diels-Alder reaction within the periphery of hierarchically assembled titanium(IV) helicates formed from mixtures of achiral, reactive and chiral, unreactive ligands was investigated in detail. Following the pathway of the chiral induction, the chiral ligands, solvents as well as substituents at the dienophile were carefully varied. Based on the results of the stoichiometric reaction, a secondary amine-catalyzed nitro-Michael reaction is performed as well which afforded reasonable diastereoselectivities.

Atropisomers of meso Tetra(N-Mesyl Pyrrol-2-yl) Porphyrins: Synthesis, Isolation and Characterization of All-Pyrrolic Porphyrins.

Atropisomerism has been observed in a variety of biaryl compounds and meso-aryl substituted porphyrins. However, in porphyrins, this phenomenon had been shown only with o-substituted 6-membered aromatic groups at the meso-position. We show herein that a 5-membered heteroaromatic (N-mesyl-pyrrol-2-yl) group at the meso-position leads to atropisomerism.