title: Rhodium carbenoid-initiated Claisen rearrangement: scope and mechanistic observations.
abstract: [formula: see text] It has been shown that alpha-diazoketones react with allylic alcohols in the presence of Rh(II) catalysts to furnish intermediate enols which subsequently undergo Claisen rearrangement to alpha-hydroxyketones. Herein we report (1) studies into the mechanism of this transformation which establish that Claisen rearrangement is neither rhodium- nor acid-catalyzed but a reaction intrinsic to the intermediate enols that proceeds at a rate governed by enol substituents (R3, R4, R5) and (2) the reaction of alpha-diazoketones with propargylic alcohols and preliminary investigations into its scope and mechanism.
authors.affiliation: Sterling Chemistry Laboratory, Yale University, New Haven, Connecticut 06520-8107, USA. john.wood@yale.edu
authors.forename: J L
authors.initials: JL
authors.lastname: Wood
authors.forename: G A
authors.initials: GA
authors.lastname: Moniz
mesh_terms: D018360:Crystallography, X-Ray; D007659:Ketones / Q000138:chemical synthesis*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D007659:Ketones; D012238:Rhodium