Palladium and Lewis-Acid-Catalyzed Intramolecular Aminocyanation of Alkenes: Scope, Mechanism, and Stereoselective Alkene Difunctionalizations.

An expansion of methodologies aimed at the formation of versatile organonitriles, via the intramolecular aminocyanation of unactivated alkenes, is herein reported. Importantly, the need for a rigid tether in these reactions has been obviated. The ease-of-synthesis and viability of substrates bearing flexible backbones has permitted for diastereoselective variants as well.

Diastereoselective Intramolecular Cyanoamidation with Alkenes.

Reported herein is a diastereoselective intramolecular alkene cyanoamidation, wherein high d.r. values are imparted by chiral directing groups.

Intramolecular oxyacylation of alkenes using a hydroxyl directing group.

Alkene oxyacylation is a new strategy for the preparation of β-oxygenated ketones. Now, with Ir catalysis and low-cost salicylate esters, alkene oxyacylation can be promoted by simple and versatile hydroxyl directing groups. This paper discusses catalyst optimization, substituent effects, mechanistic experiments, and the challenges associated with asymmetric catalysis.