title: Stereospecific cross-coupling reactions of aryl-substituted tetrahydrofurans, tetrahydropyrans, and lactones.
abstract: The stereospecific ring-opening of O-heterocycles to provide acyclic alcohols and carboxylic acids with controlled formation of a new C-C bond is reported. These reactions provide new methods for synthesis of acyclic polyketide analogs with complex stereochemical arrays. Stereoselective synthesis of the cyclic template is utilized to control relative configuration; subsequent stereospecific nickel-catalyzed ring-opening affords the acyclic product. Aryl-substituted tetrahydrofurans and tetrahydropyrans undergo nickel-catalyzed Kumada-type coupling with a range of Grignard reagents to furnish acyclic alcohols with high diastereoselectivity. Enantioenriched lactones undergo Negishi-type cross-coupling with dimethylzinc to afford enantioenriched carboxylic acids. Application in a two-step enantioselective synthesis of an anti-dyslipidemia agent is demonstrated.
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697-2025, United States.
authors.forename: Emily J
authors.initials: EJ
authors.lastname: Tollefson
authors.forename: David D
authors.initials: DD
authors.lastname: Dawson
authors.forename: Charlotte A
authors.initials: CA
authors.lastname: Osborne
authors.forename: Elizabeth R
authors.initials: ER
authors.lastname: Jarvo
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry; D002384:Catalysis; D005663:Furans / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D011714:Pyrans / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D002264:Carboxylic Acids; D005663:Furans; D007783:Lactones; D011714:Pyrans