title: Development of the Regiodivergent Asymmetric Prenylation of 3-Substituted Oxindoles.
abstract: This paper describes our efforts to design a Pd-catalyzed asymmetric prenylation of 3-substituted oxindoles that affords access to both the linear and reverse-prenylated products. Both 3-alkyl- and 3-aryloxindoles performed well under our optimized reaction conditions. The regiodivergent alkylation of monoterpene-derived electrophiles using this methodology was also investigated. The utility of this methodology in natural product synthesis was demonstrated through the efficient total syntheses of four Flustra alkaloids, which also allowed the absolute stereochemistry of the prenylated oxindole products to be assigned. Surprisingly, the same enantiomer of ligand produced linear and branched regioisomers of opposite chirality.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA, 94305, USA.
authors.forename: Barry M
authors.identifier: http://orcid.org/0000-0001-7369-9121
authors.initials: BM
authors.lastname: Trost
authors.affiliation: University of Toronto, 78 Queens Park, Toronto, ON, M5S 2C5, Canada.
authors.forename: Walter H
authors.initials: WH
authors.lastname: Chan
authors.affiliation: Discovery Chemistry, Genentech, 1 DNA Way, South San Francisco, CA, 94080, USA.
authors.forename: Sushant
authors.initials: S
authors.lastname: Malhotra
keywords: allylic alkylation; flustramines; oxindoles; palladium; prenylation