Herein, we report a chiral phosphine-triazole ligand for the Ir-catalyzed asymmetric hydrogenation of exocyclic benzofused alkenes. Overcoming previous limitations, the catalytic system is able to successfully hydrogenate exocyclic olefins bearing a benzofused five-and six-membered ring motif (ee's between 92 to 99%). The catalyst tolerates well the presence of several substituents and substitution patterns at both aromatic rings. The absence of a competing isomerization process together with the perfect fit of the olefins in the catalyst chiral pocket are key to surpass the previous limitations in the hydrogenation of both 5-and 6membered ring benzofused exocyclic olefins.

Pd‐catalyzed asymmetric allylic substitution (AAS) is a highly effective method for producing chiral molecules with alkene‐substituted frameworks which can be further derivatized. However, its stereochemical outcome is affected by the steric requirements of the substrate and only a narrow set of nucleophiles yield excellent enantioselectivities. In this regard, phosphite‐oxazolines have emerged as strong candidates to be privileged ligands for this process, providing results that surpass most of the previously published studies. They have provided high enantiocontrol when used in the Pd‐AAS of several hindered and unhindered substrates, using a wide range of C‐, O‐, and N‐nucleophiles. In this concept, we review and discuss the current progress made in the design of tailor‐made phosphite‐oxazoline ligand libraries for the Pd‐AAS of a broad range of substrates and nucleophiles and its application in the construction of chiral complex molecules.

The front cover picture is an artistic rendering illustrating the inside of the pressure reactor during an Ir‐catalyzed asymmetric hydrogenation of benzofused exocyclic olefins. The schematic orange ball represents the new simple Ir/phosphine‐triazole catalytic system which, surpassing previous limitations, hydrogenate in high enantioselectivities (ee's up to 99%) a wide range of exocyclic olefins bearing benzofused five‐ and six‐membered ring pattern. Details can be found in the Research Article by Montserrat Diéguez and co‐workers (M. Biosca, P. de la Cruz‐Sánchez, D. Tarr, P. Llanes, E. A. Karlsson, J. Margalef, O. Pàmies, M. À. Pericàs, M. Diéguez, Adv. Synth. Catal. 2023, 365, 167–177; DOI: 10.1002/adsc.202200870).