title: Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters.
abstract: Boronic acid solution speciation can be controlled during the Suzuki-Miyaura cross-coupling of haloaryl N-methyliminodiacetic acid (MIDA) boronic esters to enable the formal homologation of boronic acid derivatives. The reaction is contingent upon control of the basic biphase and is thermodynamically driven: temperature control provides highly chemoselective access to either BMIDA adducts at room temperature or boronic acid pinacol ester (BPin) products at elevated temperature. Control experiments and solubility analyses have provided some insight into the mechanistic operation of the formal homologation process.
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL (UK).
authors.forename: James W B
authors.initials: JW
authors.lastname: Fyfe
authors.affiliation: Laboratori de Química Farmacèutica, Facultat de Farmàcia and Institute of Biomedicine (IBUB), Universitat de Barcelona, Av. Joan XXIII, Barcelona, 08028 (Spain).
authors.forename: Elena
authors.initials: E
authors.lastname: Valverde
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL (UK).
authors.forename: Ciaran P
authors.initials: CP
authors.lastname: Seath
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL (UK).
authors.forename: Alan R
authors.initials: AR
authors.lastname: Kennedy
authors.affiliation: GlaxoSmithKline, Medicines Research Centre, Gunnels Wood Road, Stevenage, Hertfordshire, SG1 2NY (UK).
authors.forename: Joanna M
authors.initials: JM
authors.lastname: Redmond
authors.affiliation: GlaxoSmithKline, Medicines Research Centre, Gunnels Wood Road, Stevenage, Hertfordshire, SG1 2NY (UK).
authors.forename: Niall A
authors.initials: NA
authors.lastname: Anderson
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL (UK).. allan.watson.100@strath.ac.uk.
authors.forename: Allan J B
authors.initials: AJ
authors.lastname: Watson
mesh_terms: D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D001897:Boronic Acids; D004952:Esters
keywords: boron; chemoselectivity; cross-coupling; palladium; speciation