1073339-11-3Relevant articles and documents
Base-Free Pd-Catalyzed C?Cl Borylation of Fluorinated Aryl Chlorides
Budiman, Yudha P.,Lorenzen, Sabine,Liu, Zhiqiang,Radius, Udo,Marder, Todd B.
, p. 3869 - 3874 (2021)
Catalytic C?X borylation of aryl halides containing two ortho-fluorines has been found to be challenging, as most previous methods require stoichiometric amounts of base and the polyfluorinated aryl boronates suffer from protodeboronation, which is accele
Protodeboronation of (Hetero)Arylboronic Esters: Direct versus Prehydrolytic Pathways and Self-/Auto-Catalysis
Hayes, Hannah L. D.,Wei, Ran,Assante, Michele,Geogheghan, Katherine J.,Jin, Na,Tomasi, Simone,Noonan, Gary,Leach, Andrew G.,Lloyd-Jones, Guy C.
, p. 14814 - 14826 (2021/09/13)
The kinetics and mechanism of the base-catalyzed hydrolysis (ArB(OR)2→ ArB(OH)2) and protodeboronation (ArB(OR)2→ ArH) of a series of boronic esters, encompassing eight different polyols and 10 polyfluoroaryl and heteroaryl moieties, have been investigated by in situ and stopped-flow NMR spectroscopy (19F,1H, and11B), pH-rate dependence, isotope entrainment,2H KIEs, and KS-DFT computations. The study reveals the phenomenological stability of boronic esters under basic aqueous-organic conditions to be highly nuanced. In contrast to common assumption, esterification does not necessarily impart greater stability compared to the corresponding boronic acid. Moreover, hydrolysis of the ester to the boronic acid can be a dominant component of the overall protodeboronation process, augmented by self-, auto-, and oxidative (phenolic) catalysis when the pH is close to the pKaof the boronic acid/ester.
Copper-Catalyzed Oxidative Cross-Coupling of Electron-Deficient Polyfluorophenylboronate Esters with Terminal Alkynes
Liu, Zhiqiang,Budiman, Yudha P.,Tian, Ya-Ming,Friedrich, Alexandra,Huang, Mingming,Westcott, Stephen A.,Radius, Udo,Marder, Todd B.
supporting information, p. 17267 - 17274 (2020/12/01)
We report herein a mild procedure for the copper-catalyzed oxidative cross-coupling of electron-deficient polyfluorophenylboronate esters with terminal alkynes. This method displays good functional group tolerance and broad substrate scope, generating cro