title: Catalytic Enantioselective and Diastereoselective Allylic Alkylation with Fluoroenolates: Efficient Access to C3-Fluorinated and All-Carbon Quaternary Oxindoles.
abstract: Synthetically versatile 3,3-disubstituted fluorooxindoles exhibiting vicinal chirality centers were obtained in high yields and with excellent enantio-, diastereo-, and regioselectivity through catalytic asymmetric fluoroenolate alkylation with allylic acetates. The reaction proceeds under mild conditions and can be scaled up without compromising the asymmetric induction. The unique synthetic usefulness of the products is highlighted by the incorporation of additional functionalities and the formation of 3-fluorinated oxindoles exhibiting an array of four adjacent centers of chirality. A new C-F bond functionalization path that provides unprecedented possibilities for the stereoselective generation of a chiral quaternary carbon center in the alkaloid scaffold is introduced.
authors.affiliation: Department of Chemistry, Georgetown University, 37th and O Streets, Washington, DC, 20057, USA.
authors.forename: Kaluvu
authors.initials: K
authors.lastname: Balaraman
authors.affiliation: Department of Chemistry, Georgetown University, 37th and O Streets, Washington, DC, 20057, USA.
authors.forename: Christian
authors.initials: C
authors.lastname: Wolf
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000470:Alkaloids / Q000737:chemistry; D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D054879:Halogenation; D008968:Molecular Conformation; D000078183:Oxindoles / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000470:Alkaloids; D000498:Allyl Compounds; D000078183:Oxindoles; C498551:allyl acetate
keywords: alkaloids; homogeneous catalysis; organofluorines; quaternary chiral centers; synthetic methods