Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences , University of Ottawa , Ottawa , Ontario Canada , K1N 6N5.
Molecular Design and Synthesis, Department of Chemistry , KU Leuven , 3001 Leuven , Belgium.
J Am Chem Soc. 2019 May 1;141(17):6869-6874. doi: 10.1021/jacs.9b03280. Epub 2019 Apr 18.
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
发展了一种通过 Ni(0)催化剂作用将伯醇和有机三氟甲磺酸酯进行分子间偶联以生成酮的方法。这种氧化转化被认为是通过三个不同的催化循环的结合来实现的。两种竞争性的氧化过程通过氢转移氧化或（拟）脱卤化途径原位生成醛。当醛形成时，Ni 催化的羰基-Heck 过程能够形成关键的碳-碳键。这种罕见的醇到酮的转化的实用性通过合成各种复杂和生物活性分子得到了证明。
