Pradhan Deepak Ranjan, Pattanaik Sandip, Kishore Jugal, Gunanathan Chidambaram
School of Chemical Sciences, National Institute of Science Education and Research, HBNI, Bhubaneswar 752050, India.
Org Lett. 2020 Mar 6;22(5):1852-1857. doi: 10.1021/acs.orglett.0c00193. Epub 2020 Feb 11.
The facile oxidation of alcohols to carboxylate salts and H is achieved using a simple and readily accessible cobalt pincer catalyst (NNNCoBr). The reaction follows an acceptorless dehydrogenation pathway and displays good functional group tolerance. The amine-amide metal-ligand cooperation in cobalt catalyst is suggested to facilitate this transformation. The mechanistic studies indicate that in-situ-formed aldehydes react with a base through a Cannizzaro-type pathway, resulting in potassium hemiacetolate, which further undergoes catalytic dehydrogenation to provide the carboxylate salts and H.
使用一种简单且易于获得的钴钳形催化剂（NNNCoBr）可实现醇向羧酸盐和氢气的简便氧化。该反应遵循无受体脱氢途径，并且对官能团具有良好的耐受性。钴催化剂中的胺 - 酰胺金属 - 配体协同作用被认为有助于这种转化。机理研究表明，原位形成的醛通过坎尼扎罗型途径与碱反应，生成半乙酰酸钾，其进一步进行催化脱氢以提供羧酸盐和氢气。
