<i>cine</i>-Silylative Ring-Opening of α-Methyl Azacycles Enabled by the Silylium-Induced C–N Bond Cleavage
Jianbo Zhang, Sukbok Chang
Abstract
Described herein is the development of a borane-catalyzed cine-silylative ring-opening of α-methyl azacycles. This transformation involves four-step cascade processes: (i) exo-dehydrogenation of alicyclic amine, (ii) hydrosilylation of the resultant enamine, (iii) silylium-induced cis-β-amino elimination to open the ring skeleton, and (iv) hydrosilylation of the terminal olefin. The present borane catalysis also works efficiently for the C–N bond cleavage of acyclic tertiary amines. On the basis of experimental and computational studies, the silicon atom was elucidated to play a pivotal role in the β-amino elimination step.
Topics & Concepts
ChemistryCleavage (geology)Bond cleavageRing (chemistry)Medicinal chemistryStereochemistryOrganic chemistryCatalysisComposite materialFracture (geology)Materials scienceOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsAsymmetric Hydrogenation and Catalysis