title: Strategic Application and Transformation of ortho-Disubstituted Phenyl and Cyclopropyl Ketones To Expand the Scope of Hydrogen Borrowing Catalysis.
abstract: The application of an iridium-catalyzed hydrogen borrowing process to enable the formation of α-branched ketones with higher alcohols is described. In order to facilitate this reaction, ortho-disubstituted phenyl and cyclopropyl ketones were recognized as crucial structural motifs for C-C bond formation. Having optimized the key catalysis step, the ortho-disubstituted phenyl products could be further manipulated by a retro-Friedel-Crafts acylation reaction to produce synthetically useful carboxylic acid derivatives. In contrast, the cyclopropyl ketones underwent homoconjugate addition with several nucleophiles to provide further functionalized branched ketone products.
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Oxford OX1 3TA, United Kingdom.
authors.forename: James R
authors.initials: JR
authors.lastname: Frost
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Oxford OX1 3TA, United Kingdom.
authors.forename: Choon Boon
authors.initials: CB
authors.lastname: Cheong
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Oxford OX1 3TA, United Kingdom.
authors.forename: Wasim M
authors.initials: WM
authors.lastname: Akhtar
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Oxford OX1 3TA, United Kingdom.
authors.forename: Dimitri F J
authors.initials: DF
authors.lastname: Caputo
authors.affiliation: GlaxoSmithkline, Medicines Research Centre , Stevenage SG1 2NY, United Kingdom.
authors.forename: Neil G
authors.initials: NG
authors.lastname: Stevenson
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Oxford OX1 3TA, United Kingdom.
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Donohoe