Acceptorless Dehydrogenative α-Olefination of Nitriles with Alcohols: Emerging Catalytic Strategies

Nitriles are fundamental functional groups in organic synthesis, serving as versatile precursors to amides, amines, acids, and heterocycles, and play a central role in pharmaceutical and materials chemistry. Among nitrile derivatives, α-olefinated nitriles are particularly valuable intermediates due to their high synthetic versatility and broad applicability. In recent years, acceptorless dehydrogenative coupling (ADC) of alcohols with nitriles has emerged as an attractive and sustainable strategy for accessing these compounds, enabling C-C bond formation with the generation of only H₂ and H₂O as by-products. Despite growing interest in this area, a comprehensive overview of αolefinated nitrile synthesis via ADC pathways has been lacking. This review provides an up-to-date summary of recent advances in transition-metal-catalyzed, earth-abundant metal-based, and photochemical approaches to nitrile olefination, with particular emphasis on ADC processes. Key developments in catalyst design, mechanistic understanding, and reaction selectivity are discussed, along with current challenges and future perspectives. By exploring these catalytic pathways, this review aims to inspire the development of novel and sustainable methods for α-olefinated nitrile synthesis from readily available feedstocks.