Key Lab of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310028, China.
Nat Commun. 2017 May 15;8:15240. doi: 10.1038/ncomms15240.
The synthesis of organic nitriles without using toxic cyanides is in great demand but challenging to make. Here we report an environmentally benign and cost-efficient synthesis of nitriles from the direct oxidative cyanation of primary carbon-hydrogen bonds with easily available molecular oxygen and urea. The key to this success is to design and synthesize manganese oxide catalysts fixed inside zeolite crystals, forming a manganese oxide catalyst with zeolite sheath (MnO@S-1), which exhibits high selectivity for producing nitriles by efficiently facilitating the oxidative cyanation reaction and hindering the side hydration reaction. The work delineates a sustainable strategy for synthesizing nitriles while avoiding conventional toxic cyanide, which might open a new avenue for selective transformation of carbon-hydrogen bonds.
有机腈的合成无需使用有毒的氰化物，这一需求十分迫切，但目前的合成方法具有挑战性。在这里，我们报道了一种环境友好且经济高效的方法，可直接利用易得的氧气和尿素将伯碳氢键氧化氰化来合成腈。这一成功的关键是设计和合成固定在沸石晶体内部的氧化锰催化剂，形成具有沸石壳层的氧化锰催化剂（MnO@S-1），该催化剂高效促进氧化氰化反应，同时阻碍副反应——水解反应，从而具有很高的腈选择性。这项工作为合成腈而避免使用传统有毒氰化物描绘了一条可持续的策略，这可能为选择性转化碳氢键开辟了一条新途径。
