镍催化叔烷基亲电试剂参与碳碳键还原偶联反应研究

Nickel-catalyzed Carbon-carbon Bond Formation via Reductive Couplings of Tertiary Alkyl Electrophiles

镍金属催化的还原偶联反应可直接利用来源广泛、价格低廉的亲电试剂作为偶联底物,具有反应条件温和、能允许反应中存在少量水和空气、官能团兼容性好等优点。含有季碳结构的化合物广泛存在于多种药物和生物活性的分子中。叔烷基亲电试剂由于空间位阻大、反应活性低、在反应中容易生成其他副产物,作为底物参与还原偶联反应仍具挑战。综述了近十年关于叔烷基亲电试剂作为底物参与的碳碳键还原偶联反应研究进展,讨论了不同催化反应中底物范围及机理。

The nickel-catalyzed reductive coupling could directly use a wide range of inexpensive electrophiles as the coupling substrates, which has the advantages of mild reaction conditions, water-and air-insensitive, and shows good tolerance to functional groups.All-carbon quaternary scaffolds are prevalent in drugs and biologically active molecules.As a result of the high steric hindrance, low reactivity, and tendency to generate byproducts in the reactions, it is a challenge for the transformation of tertiary alkyl electrophiles in reductive couplings.Summarized the research progress in recent ten years of nickel-catalyzed carbon-carbon bond-forming reductive couplings, which involving the tertiary alkyl electrophiles as the substrates.The range of substrates and mechanisms of different catalytic systems were discussed.