摘要：Chakreshwara Kuloor[a], Akash[a], VishakhaGoyal[a, b],Radek Zbořil[b,c]*,Mathias Beller[a]*, Rajenahally V. Jagadeesh[a, b]*

转自：康龙化成

Nickel-catalyzed ReductiveHydrolysis of Nitriles to Alcohols

Chakreshwara Kuloor[a], Akash[a], VishakhaGoyal[a, b],Radek Zbořil[b,c]*,Mathias Beller[a]*, Rajenahally V. Jagadeesh[a, b]*

[a] Leibniz-Institut für Katalyse,Albert-Einstein-Straße 29a,18059 Rostock, Germany

[b] Nanotechnology Centre, Centre forEnergy and Environmental Technologies, VŠB–Technical University of Ostrava,Ostrava-Poruba,Czech Republic

[c] Regional Centre of Advanced Technologies and Materials,Czech Advanced Technology and Research Institute, PalackýUniversity Olomouc, Šlechtitelů 27,Olomouc, 783 71, Czech Republic.

—Angew.Chem. Int. Ed. 2024, doi: 10.1002/anie.202414689

Recommended by Depei Meng_MC4

KEYWORDS: Hydrolysis(反应类型), Nicatalysis (反应类型),C(sp3)–O (成键类型), Nitriles (原料),Alcohols (产物),Ni(OTf)2-Triphos (催化剂)

ABSTRACT: Herewe report Ni-catalyzed reductive hydrolysis of nitriles to alcohols in thepresence of molecular hydrogen. This conversion likely occurs in a dominoreaction sequence that first involves the hydrogenation of nitrile to primaryimine, then the hydrolysis of imine, and subsequent deamination to thealdehyde, which is finally hydrogenated to the desired alcohol. Crucial forthis reductive hydrolysis process is the commercially available triphos-ligatedNi-complex that enables highly efficient and selective transformation ofaromatic, heterocyclic, and aliphatic nitriles including fatty nitriles toprepare functionalized primary alcohols. Further, the synthetic applicabilityof this Ni-based protocol is presented for the selective conversion of nitrileto alcoholic group in structurally diverse and complex drug molecules as wellas agrochemicals. The resulting products, alcohols are indispensable chemicalscommonly used in organic synthesis and life sciences as well as material andenergy technologies.

Catalyticreductions of nitriles to prepare other valuable products

Catalyticconversion of nitriles to different products: Competition between reductivehydrolysis vs hydrogenation vs hydration/hydrolysis.

Selected Scope

Showcasinglate-stage functionalizations

Inconclusion, Chakreshwara Kuloor etal. demonstrateda general methodology based on earth abundant metal catalyst that empowered highlyefficient and selective conversion of a broad range of nitriles tocorresponding alcohols. Inthe presence of in situ generated Ni-triphos (Ni-L2) complex, the reductivehydrolysis of aromatic, heterocyclic and aliphatic nitriles including fattynitriles produced a range of functionalized, and structurally diverse primaryalcohols. Notably, this Ni-based protocol can be applied for the late-stagefunctionalization of life science molecules by converting nitrile groups intoalcohol groups in structurally complex bioactive molecules.

总地来说，Chakreshwara Kuloor等报道了一种基于廉价的镍催化剂，高效、选择性地将多种腈转化为相应的醇的通用方法。在原位生成的三磷镍(Ni-L2)络合物的存在下，芳香族、杂环族和脂肪族腈(包括脂肪腈)均可被还原水解产生官能化和结构多样的伯醇。值得注意的是，方法也可将结构复杂的生物活性分子中的腈基转化为醇基，展现了用于药物分子的后期功能化的潜力。

来源：新浪财经