Chiral N-heterocyclic carbene catalyzed, enantioselective oxodiene Diels-Alder reactions with low catalyst loadings.
Chiral N-heterocyclic carbene (NHC) catalyzed redox reactions of racemic alpha-chloroaldehydes lead to the generation of chiral enolates suitable for highly enantioselective inverse-electron-demand 1-oxodiene Diels-Alder reactions. Significantly, these reactions proceed under mild, operationally friendly reaction conditions (EtOAc, room temperature, 2-8 h) using less than 1 mol % of a chiral N-mesityl triazolium salt as the precatalyst. A broad array of densely functionalized dihydropyran-2-ones bearing either aliphatic or aromatic substiutents are formed in excellent yields and exceptional enantioselectivities from readily available reactants. Stereochemical mismatching between the racemic starting materials and the chiral catalyst is avoided by rapid epimerization of the chloroaldehydes under the reaction conditions.
He
Ming
M
Department of Chemistry and Biochemistry, University of California at Santa Barbara, California 93106-9510, USA.
Uc
Gerson J
GJ
Bode
Jeffrey W
JW
D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006838:Hydrocarbons / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis*; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D013237:Stereoisomerism
D000447:Aldehydes; D000475:Alkenes; D006571:Heterocyclic Compounds; D006838:Hydrocarbons; D007659:Ketones; D007783:Lactones; C030011:carbene; D008697:Methane