The regioselectivity of the Diels–Alder reaction between ω‐substituted dienoates and unsymmetrical dienophiles can be strictly controlled by “calixarene‐like” metal complexes of type A (see scheme). The reaction of the dienoate coligand in A with acrylonitrile leads to the exclusive formation of the regioisomer adduct I, which is in striking contrast to the low regioselectivity of the background reaction.
The synthesis and characterization of two new macrobicyclic azathioether ligands are reported. The biphenyl-based compounds were prepared by traditional organic reactions and cyclization methods. The identity of one compound was confirmed by X-ray crystallography.
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