Direct Deoxyarylation of Non‐Activated Alcohols

Abstract The formation of carbon–carbon bonds constitutes the most critical fundamental reaction in organic synthesis. Although synthetic chemists have achieved significant advancements in the cross‐coupling of stable C(sp 3 ) substrates, such as aliphatic carboxylic acids and alkyl halides, cost‐effective, accessible, and versatile sources of alkyl groups, specifically alcohols, remain underutilized. The direct deoxygenation of alcohols under mild circumstances presents a significant challenge in organic synthesis, primarily due to the absence of an efficient mechanism for the direct activation of C─O bonds. Consequently, there is an imperative necessity for chemists to devise a multifaceted approach for the cross‐coupling of alcohols. This study aims to utilize neutral diphenylboron radicals as hydroxyl activation agents to directly activate the carbon–oxygen bonds of prevalent alcohols, thereby generating alkyl radicals, which are subsequently involved in nickel‐catalyzed arylation processes. Both free alcohols and aryl bromides, which are easily accessible compounds, can serve as coupling partners directly without requiring pre‐functionalization. The direct arylation process of alcohols exhibits a broad substrate scope, as demonstrated by the subsequent arylation of several structurally intricate natural compounds and pharmaceuticals.