Stereoselectivity in oxyallyl–furan (4 + 3) cycloadditions: control of intermediate conformations and dispersive stabilisation in cycloadditions involving oxazolidinone auxiliaries
- 25 June 2010
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Chemical Science
- Vol. 1 (3) , 387-392
Abstract
Chiral oxazolidinones were previously thought to control cycloaddition stereoselectivity by steric crowding of one face of the substrate. We have discovered that in (4 + 3) cycloaddition reactions of oxyallyls, the stereoinduction is caused instead by stabilising CH–π interactions that lead to reaction at the more crowded face of the oxyallyl. Density functional theory calculations on the (4 + 3) cycloadditions of oxazolidinone-substituted oxyallyls with furans establish unexpected transition state conformations and a new explanation of selectivity.Keywords
This publication has 46 references indexed in Scilit:
- An Alternative Mechanism for Diels–Alder Reactions of Evans Auxiliary DerivativesChemistry – A European Journal, 2009
- Density Functionals with Broad Applicability in ChemistryAccounts of Chemical Research, 2008
- Semiempirical GGA‐type density functional constructed with a long‐range dispersion correctionJournal of Computational Chemistry, 2006
- New Chiral Auxiliaries for Dynamic Kinetic Resolution: From Theory to ExperimentChemistry – A European Journal, 2004
- Accurate description of van der Waals complexes by density functional theory including empirical correctionsJournal of Computational Chemistry, 2004
- Helium dimer dispersion forces and correlation potentials in density functional theoryThe Journal of Chemical Physics, 2002
- The Origin of endo Stereoselectivity in the Hetero-Diels–Alder Reactions of Aldehydes with ortho-Xylylenes: CH–π, π–π, and Steric Effects on StereoselectivityChemistry – A European Journal, 2002
- Controlling Self‐AssemblyChemistry – A European Journal, 1997
- A Theoretical Study of the Endo/Exo Selectivity of the Diels−Alder Reaction between Cyclopropene and ButadieneJournal of the American Chemical Society, 1997
- Development of the Colle-Salvetti correlation-energy formula into a functional of the electron densityPhysical Review B, 1988