Carbonyl-Ene Reactions Catalyzed by Bis(oxazoline) Copper(II) Complexes Proceed by a Facile Stepwise Mechanism: DFT and ONIOM (DFT:PM3) Studies.

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Abstract

The mechanism of a carbonyl-ene addn. reaction catalyzed by a bis(oxazoline) copper(II) complex has been studied using DFT methods. We find that the reaction proceeds by a stepwise mechanism with very low barriers and have identified the role of the metal catalyst. We find that the more computationally economic ONIOM method gives accurate geometries for the stationary structures on the potential energy surface but that accurate energetics must be calcd. at the full DFT level. [on SciFinder (R)]

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Density functional theory (B3LYP, UB3LYP DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Potential barrier Potential energy surface Stereochemistry Transition state structure (DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Alkenes Carbonyl compounds Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) PM3 (ONIOM (DFT:PM3) DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Bond formation (carbon-carbon, leading to zwitterion DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Addition reaction Addition reaction catalysts (ene DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Hydrogen shift (in zwitterionic intermediate DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Molecular structure (of potential surface species DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Complexation (of substrates DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Free energy (potential surface DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism) Cyclization (to oxetane, neither kinetically nor thermodynamically favored DFT and ONIOM (DFT:PM3) studies of carbonyl-ene reactions catalyzed by bis(oxazoline) copper(II) complexes that proceed by a facile stepwise mechanism)

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