Palladium-Catalyzed γ,γ'-Diarylation of Free Alkenyl Amines.

The direct difunctionalization of alkenes is an effective way to construct multiple C-C bonds in one-pot using a single functional group. The regioselective dicarbofunctionalization of alkenes is therefore an important area of research to rapidly obtain complex organic molecules. Herein, we report a palladium-catalyzed γ,γ'-diarylation of free alkenyl amines through interrupted chain walking for the synthesis of Z-selective alkenyl amines. Notably, while 1,3-dicarbofunctionalization of allyl groups is well precedented, the present disclosure allows 1,3-dicarbofunctionalization of highly substituted allylamines to give highly Z-selective trisubsubstituted olefin products. This cascade reaction operates via an unprotected amine-directed Mizoroki-Heck (MH) pathway featuring a ß-hydride elimination to selectively chain walk to furnish a new terminal olefin which then generates the cis-selective alkenyl amines around the sterically crowded allyl moiety. This operationally simple protocol is applicable to a variety of cyclic, branched, and linear secondary and tertiary alkenylamines, and has a broad substrate scope with regard to the arene coupling partner as well. Mechanistic studies have been performed to help elucidate the mechanism, including the presence of a likely unproductive side C-H activation pathway.

One-dimensional networks formed via the self-assembly of anthracenedibenzoic acid with zinc(II).

Self-assembly of metal-organic coordination polymers occurs because of enthalpically favorable interactions. In the case of the bulky 4,4'-(anthracene-9,10-diyl)dibenzoic acid ligand (abdH2), we demonstrate that the presence of numerous π-π and C-H...π interactions outweigh the formation of saturated coordination complexes with zinc, leading to the formation of a dimethylformamide (DMF) solvate, namely 4,4'-(anthracene-9,10-diyl)dibenzoic acid dimethylformamide disolvate, C28H18O4·2C3H7NO or [(abdH2)(DMF)2], at low concentrations of zinc. Meanwhile, at higher zinc concentrations, the abdH2 ligand gives rise to the nonporous one-dimensional coordination polymer catena-poly[[bis(dimethylformamide-κO)zinc(II)]-µ-4,4'-(anthracene-9,10-diyl)dibenzoato-κ2O:O'], [Zn(C28H16O4)(C3H7NO)2]n or [Zn(abd)(DMF)2]n, when assembled in dimethylformamide, while a related compound is observed when N,N-dimethylacetamide (DMA) is used as the solvent, namely catena-poly[[[bis(N,N-dimethylacetamide-κO)zinc(II)]-µ-4,4'-(anthracene-9,10-diyl)dibenzoato-κ2O:O'] N,N-dimethylacetamide monosolvate], {[Zn(C28H16O4)(C4H9NO)2]·C4H9NO}n or {[Zn(abd)(DMA)2]·DMA}n. Attempts to use other amide-based solvents did not give rise to any other assembled structures.