title: Directed metal (oxo) aliphatic C-H hydroxylations: overriding substrate bias.
abstract: The first general strategy for a directing effect on metal (oxo)-promoted C-H hydroxylations is described. Carboxylic acid moieties on the substrate overcome unfavorable electronic, steric, and stereoelectronic biases in C-H hydroxylations catalyzed by the non-heme iron complex Fe(PDP). In a demonstration of the power of this directing effect, C-H oxidation is diverted away from an electronically favored C-1 H abstraction/rearrangement pathway in the paclitaxel framework to enable installation of C-2 oxidation in the naturally occurring oxidation state and stereoconfiguration.
authors.affiliation: Department of Chemistry, Roger Adams Laboratory, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Marinus A
authors.initials: MA
authors.lastname: Bigi
authors.forename: Sean A
authors.initials: SA
authors.lastname: Reed
authors.forename: M Christina
authors.initials: MC
authors.lastname: White
mesh_terms: D001952:Bridged-Ring Compounds / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D004583:Electrons; D005296:Ferrous Compounds / Q000737:chemistry*; D006900:Hydroxylation; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D043823:Taxoids / Q000737:chemistry
chemical_list: D001952:Bridged-Ring Compounds; D002264:Carboxylic Acids; D005296:Ferrous Compounds; D043823:Taxoids; C080625:taxane