title: Pd(II)-catalyzed spiroketalization of ketoallylic diols.
abstract: A high-yielding stereoselective method for forming spiroketals from simple ketoallylic diols is reported. Employing catalytic [PdCl2(MeCN)2] in THF at 0 °C, these dehydrative cyclization reactions require only mild conditions to produce vinyl-substituted spiroketals in high yields after brief reaction times with water as the only byproduct. Using this method, the stereochemical information embedded at the nucleophile is transmitted "down-the-chain" and efficiently sets the stereochemistry at both the anomeric carbon atom and the newly formed allylic stereocenter.
authors.affiliation: Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611, USA.
authors.forename: Jean A
authors.initials: JA
authors.lastname: Palmes
authors.forename: Paulo H S
authors.initials: PH
authors.lastname: Paioti
authors.forename: Leonardo Perez
authors.initials: LP
authors.lastname: de Souza
authors.forename: Aaron
authors.initials: A
authors.lastname: Aponick
mesh_terms: D002384:Catalysis; D005663:Furans / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013141:Spiro Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D005663:Furans; D013141:Spiro Compounds; C520774:spiroketal; D010165:Palladium; C008756:palladium chloride
keywords: anomeric effect; catalysis; ketoallylic diols; palladium; spiroketalization