Nickel Catalyzed Selective Arylation of Geminal Dinitriles: Direct Access to α-Cyano Carbonyl Compounds.

The catalytic intermolecular arylation of disubstituted geminal dinitriles with in situ generated arylnickel complexes is disclosed. This method efficiently provides various all-carbon substituted α-cyanocarbonyl compounds without additives and an inert atmosphere. It also demonstrates the arylation of R-BINOL and S-BINOL derived geminal dinitriles, preserving optical purity. Mechanistic studies proved that the in situ generated organonickel complex is involved in arylation.

Nickel-Catalyzed Domino Reaction of α-Aryloxyacetonitriles with Arylboronic Acids: Synthesis of 2-Aroylbenzo[b]furans.

We disclose the first catalytic domino reaction of α-(2-formylaryloxy)acetonitriles with arylboronic acids, yielding a range of 2-aroylbenzo[b]furans with yields of up to 93%. Ni(acac)2 serves as an effective dual catalyst. The protocol is also applicable to α-(2-acetylphenoxy)acetonitrile, giving rise to 3-methyl-2-aroylbenzo[b]furans. This domino process is efficient, additive-free, and compatible with a variety of aryl boronic acids, including those with CF3, NO2, CN, and CO2Me groups. Mechanistic studies highlight the dual activation facilitated by the nickel catalyst.

Cu(OTf)2 Enhanced Intramolecular Nucleophilic N-Arylation of 2-Amino-3-arylquinolines.

In the presence of Cu(OTf)2 (5 mol %) and KOtBu, a synergistic effect of the N-arylation process on 2-amino-3-arylquinolines is observed. Within 4 h, this method provides a wide variety of norneocryptolepine analogues with good to excellent yields. Overall, a double heteroannulation strategy for the synthesis of indoloquinoline alkaloids from nonheterocyclic precursors is demonstrated. Mechanistic investigations establish that the reaction proceeds via the SNAr pathway. Despite moderate yields, the one-pot, two-step double heteroannulation illustrates that this procedure is highly atom-efficient. Neocryptolepine, a natural product, is also synthesized from indoloquinoline. A brief study of the photophysical properties of selected norneocryptolepine analogues is also discussed.

Chemoselective Ullmann Reaction of α-Trisubstituted Thioamides: Synthesis of Novel 2-Iminobenzothiolanes.

New classes of unexplored benzo[b]thiolanes are synthesized from trisubstituted thioamides through copper-catalyzed intramolecular S-arylation of thioamides for the first time. This method provides good to excellent yields with fully controlled chemoselectivity. Unusually, iminobenzo[b]thiolanes are very stable under mild acidic conditions. A plausible mechanism is proposed for the chemoselective S-arylation process.