美国北卡罗来纳大学教堂山分校Alexander J. M. Miller团队报道了咪唑衍生卡宾及其盐促进镍催化的酯羰基化反应。相关研究成果发表在2023年11月17日出版的国际学术期刊《科学》。

每年生产数百万吨乙酰基衍生物，如乙酸和乙酸酐。这些化学工业的基石被加工成酯类、酰胺类，最终形成聚合物材料、药品和其他消费品。大多数乙酰基在工业上使用均相贵金属催化剂生产，主要是铑和铱络合物。

该文中，研究人员发现丰富的镍可以与咪唑衍生的卡宾或相应的盐配对，催化转换频率（TOF）超过150h^-1，转换数（TON）超过1600的甲酯羰基化，这些基准值可与最先进的铑基系统相媲美，并大大超过已知的三苯基膦基镍催化剂，其在相同条件下以TOF~7h^-1和TON~100运行。

附：英文原文

Title: Nickel-catalyzed ester carbonylation promoted by imidazole-derived carbenes and salts

Author: Changho Yoo, Shrabanti Bhattacharya, Xin Yi See, Drew W. Cunningham, Sebastian Acosta-Calle, Steven T. Perri, Nathan M. West, Dawn C. Mason, Chris D. Meade, Christopher W. Osborne, Phillip W. Turner, Randall W. Kilgore, Jeff King, Jeffrey H. Cowden, Javier M. Grajeda, Alexander J. M. Miller

Issue&Volume: 2023-11-17

Abstract: Millions of tons of acetyl derivatives such as acetic acid and acetic anhydride are produced each year. These building blocks of chemical industry are elaborated into esters, amides, and eventually polymer materials, pharmaceuticals, and other consumer products. Most acetyls are produced industrially using homogeneous precious metal catalysts, principally rhodium and iridium complexes. We report here that abundant nickel can be paired with imidazole-derived carbenes or the corresponding salts to catalyze methyl ester carbonylation with turnover frequency (TOF) exceeding 150 hour–1 and turnover number (TON) exceeding 1600, benchmarks that invite comparisons to state-of-the-art rhodium-based systems and considerably surpass known triphenylphosphine-based nickel catalysts, which operate with TOF ~7 hour–1 and TON ~100 under the same conditions.

DOI: ade3179

Source: https://www.science.org/doi/10.1126/science.ade3179