DFT Studies of Mechanism and Origin of Stereoselectivity of Palladium-Catalyzed Cyclotrimerization Reactions Affording syn-Tris(norborneno)benzenes
Citations Over TimeTop 19% of 2014 papers
Abstract
Pd-catalyzed cyclotrimerization reactions of enantiopure halonorbornene derivatives furnished C3 or C3v symmetric syn-tris(norborneno)benzenes with high syn selectivity. To elucidate the reaction mechanism as well as the stereoselectivity of the present Pd-catalyzed cyclotrimerization, DFT calculations were carried out. The promising reaction pathway consists of (1) sequential olefin insertion followed by an HX elimination reaction of halonorbornene with the norbornenylpalladium intermediate, (2) electrocyclization of the trienylpalladium intermediate with a lower activation barrier than a triene compound, and (3) the β-elimination of HPdX of the cyclohexadienylpalladium intermediate. In addition, the stereoselectivity would be controlled by the regioselectivity in the olefin insertion process (homo and hetero positions) and the symmetry breaking in the palladacyclic intermediate.
Related Papers
- → Synthesis of Enantiopure γ‐Lactones via a RuPHOX‐Ru Catalyzed Asymmetric Hydrogenation of γ‐Keto Acids(2018)26 cited
- → Synthesis of Enantiopure 5-Substituted 2,3-Methanopyrrolidines by Cyclization of Enantiopure α-Branched α-N-Homoallylamino Nitriles(2012)8 cited
- → A Valuable Synthetic Route to the Enantiopure Functionalized N‐Substituted Aziridines(2004)1 cited
- → ChemInform Abstract: Efficacious and Rapid Metal‐ and Solvent‐Free Synthesis of Enantiopure Oxazolines.(2015)
- → ChemInform Abstract: Chiral Pyridin‐3‐ones and Pyridines: Syntheses of Enantiopure 2,4‐Disubstituted 6‐Hydroxy‐1,6‐dihydro‐2H‐pyridin‐3‐ones, 2,3‐Disubstituted 4‐Iodopyridines, and Enantiopure 2,3‐Disubstituted 4‐Pyridinemethanols.(2012)