Tandem Dearomatization/Enantioselective Allylic Alkylation of Pyridines
Steffen Greßies, Lars Süße, Tyler D. Casselman, Brian M. Stoltz
Abstract
High Resolution Image Download MS PowerPoint Slide Herein, we report a multistep one-pot reaction of substituted pyridines leading to N -protected tetrahydropyridines with outstanding enantioselectivity (up to 97% ee). An iridium(I)-catalyzed dearomative 1,2-hydrosilylation of pyridines enables the use of N -silyl enamines as a new type of nucleophile in a subsequent palladium-catalyzed asymmetric allylic alkylation. This telescoped process overcomes the intrinsic nucleophilic selectivity of pyridines to synthesize enantioenriched, C-3-substituted tetrahydropyridine products that have been otherwise challenging to access.
Topics & Concepts
ChemistryNucleophileEnantioselective synthesisTsuji–Trost reactionAllylic rearrangementHydrosilylationIridiumAlkylationSilylationCatalysisCombinatorial chemistryTandemSelectivityNucleophilic additionPalladiumOrganic chemistryComposite materialMaterials scienceAsymmetric Synthesis and CatalysisCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and Catalysis