Mechanistic Model for Enantioselective Intramolecular Alkene Cyanoamidation via Palladium-Catalyzed C-CN Bond Activation.

We studied key aspects of the mechanism of Pd-catalyzed C-CN bond activation and intramolecular enantioselective alkene cyanoamidation. An Abboud-Abraham-Kamlet-Taft (AAKT) linear solvation energy relationship (LSER) model for enantioselectivity was established. We investigated the impact of Lewis acid (BPh), Lewis base (DMPU), and no additives.

Palladium catalyzed intramolecular acylcyanation of alkenes using α-iminonitriles.

Reported here is a palladium catalyzed intramolecular acylcyanation of alkenes using α-iminonitriles. Through this method, highly functionalized indanones are synthesized in moderate to high yields using Pd(PPh3)4, without need for any additional ligands, and a common Lewis acid (ZnCl2). Additionally, the reaction tolerates substitution at various positions on the aromatic ring including electron donating and electron withdrawing groups.

Intramolecular polar [4(⊕)+2] cycloadditions of aryl-1-aza-2-azoniaallene salts: unprecedented reactivity leading to polycyclic protonated azomethine imines.

The first example of aryl-1-aza-2-azoniaallene salts undergoing a [4 + 2]-cycloaddition reaction in which the azo bond and one aromatic π-bond make up the 4π component is described. This intramolecular reaction appears to be concerted and provides high yields of protonated azomethine imine products that contain a 1,2,3,4-tetrahydrocinnoline core. Substituted alkenes provided products that contain all carbon or nitrogen bearing quaternary centers in high yield.