Ru-catalyzed activation of free phenols in a one-step Suzuki–Miyaura cross-coupling under mechanochemical conditions

Abstract

Activation of phenols by a Ru-catalyst allows for the resulting η⁵-phenoxo complex to selectively react with a variety of nucleophiles under mechanochemical conditions. Conversion of phenolic hydroxy groups without derivatization is important for late-stage modifications of pharmaceuticals and in the context of lignin-material processing. We present a one-step, Ru-catalyzed cross-coupling of phenols with boronic acids, aryl trialkoxysilanes and potassium benzoyltrifluoroborates under mechano-chemical conditions. The protocol accepts a wide scope of starting materials and allows for gram-scale synthesis in excellent yields. The developed approach constitutes a very interesting and waste-limiting alternative to the known methods.