Sodium Butylated Hydroxytoluene: A Functional Group Tolerant, Eco‐Friendly Base for Solvent‐Free, Pd‐Catalysed Amination
Volodymyr Semeniuchenko, Wilfried M. Braje, Michael G. Organ
Abstract
NaBHT (sodium 2,6-di-tert-butyl-4-methylphenolate), a strong, but hindered and lipophilic base, has been effectively paired with similarly lipophilic, high-reactivity Pd-NHC (N-heterocyclic carbene) catalysts to produce an ideal combination for performing solvent-free (melt) cross-coupling amination. The mild nucleophilicity of NaBHT, coupled with the anti-oxidant properties of its conjugate acid byproduct, BHT means the process seems to have no functional group incompatibilities. Highly effective coupling of base-sensitive and redox-active functional groups was observed in all cases with only 0.1-0.2 mol percent catalyst. Comparisons using the standard base for this reaction, KOtBu, led to poor couplings or complete degradation in most applications - only NaBHT works.