Substituent effects on aryltrifluoroborate solvolysis in water: Implications for Suzuki-Miyaura coupling and the design of stable 18F-labeled aryltrifluoroborates for use in PET imaging

Article abstract of DOI:10.1021/jo800681d

(Chemical Equation Presented) Whereas electron withdrawing substituents retard the rate of aryltrifluoroborate solvolysis, electron-donating groups enhance it. Herein is presented a Hammett analysis of the solvolytic lability of aryltrifluoroborates where log(K_solv) values correlate to a values with a ρ value of approximately -1. This work provides a predictable rubric for tuning the reactivity of boron for several uses including ¹⁸F-labeled PET reagents and has mechanistic implications for ArBF₃-enhanced ligandless metal-mediated cross coupling reactions with aryltrifluoroborates.