Deoxygenative Suzuki–Miyaura arylation of tertiary alcohols through silyl ethers

Conventional Suzuki–Miyaura arylations use halogenated compounds as electrophilic coupling partners. Although the catalytic activation of organohalides is well established, these substrates are seldom naturally abundant and questions exist to their metabolic environmental friendliness. Owing existence readily available chemical feedstocks, alcohols highly desirable cross-coupling partners, although pathways activate strong C–O bond rarer. Here tertiary with boronic esters through in situ alcohol silylation described, providing access quaternary carbon scaffolds without needing proceed by an activated alkyl halide or pseudohalide intermediate. A dual catalyst system used both Ni(0) Bi(III) components playing a critical role, along mild chlorosilane reactant. This method was found tolerate diverse functional groups including chloro, nitro, olefin, ketone, ester phenol moieties, while also being applicable derivatization heterocyclic scaffolds. Mechanistic studies suggest combination Lewis acid organosilane promote heterolytic cleavage substrate generate intermediate, powerful strategy for derivatizing alcohols. Alkyl attractive surrogates halides reactions, but methods underdeveloped. Now Ni-catalysed arylation reported that uses aryl alcohols, silylation.