Enantioselective Narasaka-Heck cyclizations: synthesis of tetrasubstituted nitrogen-bearing stereocentersElectronic supplementary information (ESI) available: Experimental procedures and characterisation data for all compounds are provided. CCDC 1438659 and 1438660. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc04466b

The first examples of highly enantioselective Narasaka-Heck cyclizations are described. A SPINOL-derived P,N-ligand system enables Pd-catalyzed 5- exo cyclization of a range of oxime esters with sterically diverse trisubstituted alkenes to generate dihydropyrroles containing tetrasubstituted nitrogen-bearing stereocenters in 56 to 86% yield and 90 : 10 to 95 : 5 e.r. These processes are rare examples of reactions that proceed via enantioselective migratory insertion of alkenes into Pd-N bonds, and the first where trisubstituted alkenes are used to generate tetrasubstituted stereocenters with high enantioselectivity. A SPINOL-derived P,N-ligand system enables Pd-catalyzed 5- exo cyclization of oxime esters with trisubstituted alkenes to generate dihydropyrroles in up to 86% yield and 95 : 5 e.r.