Speciation Control During Suzuki-Miyaura Cross-Coupling of Haloaryl and Haloalkenyl MIDA Boronic Esters

• Published in: Chemistry : a European journal Vol. 21; no. 24; pp. 8951 - 8964
• Main Authors: Fyfe, James W. B., Valverde, Elena, Seath, Ciaran P., Kennedy, Alan R., Redmond, Joanna M., Anderson, Niall A., Watson, Allan J. B.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 08.06.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Access control; Acids; boron; Boronic Acids - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; chemoselectivity; Control; Cross coupling; Derivatives; Esters; Esters - chemistry; Homology; Molecular Structure; palladium; Physical Sciences; Science & Technology; Solubility; Speciation; chemoselectivity; GENERAL-SOLUTION; ACID; PROTODEBORONATION; BICYCLIC DERIVATIVES; ELECTROPHILIC DISPLACEMENT-REACTIONS; EFFICIENT SYNTHESIS; VERSATILE BUILDING-BLOCK; KINETIC EVIDENCE; speciation; cross-coupling; TETRACOORDINATED BORON; palladium; SELECTIVE SYNTHESIS; boron
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201500970

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. Controlled coupling: Boronic acid solution speciation can be controlled during the Suzuki–Miyaura cross‐coupling of haloaryl N‐methyliminodiacetic acid (MIDA) boronic esters to enable chemoselective access to either BMIDA or boronic acid pinacol ester (BPin) products. The reaction is contingent upon control of the basic biphase and product distribution can be controlled by temperature regulation.