Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters

Fyfe, James W. B. and Valverde, Elena and Seath, Ciaran P. and Kennedy, Alan R. and Redmond, Joanna M. and Anderson, Niall A. and Watson, Allan J. B. (2015) Speciation control during Suzuki-Miyaura cross-coupling of haloaryl and haloalkenyl MIDA boronic esters. Chemistry - A European Journal, 21 (24). 8951–8964. ISSN 0947-6539

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    Abstract

    Boronic acid solution speciation can be controlled during the Suzuki-Miyaura cross-coupling of haloaryl 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 BPin products at elevated temperature. Control experiments and solubility analyses have provided some insight into the mechanistic operation of the formal homologation process.