Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden.
Current address: Institute of Technical Biocatalysis, Hamburg University of Technology TUHH, 21071, Hamburg, Germany.
Angew Chem Int Ed Engl. 2020 Mar 23;59(13):5403-5406. doi: 10.1002/anie.202000054. Epub 2020 Feb 19.
We report the first Fe -catalyzed biomimetic aerobic oxidation of alcohols. The principle of this oxidation, which involves several electron-transfer steps, is reminiscent of biological oxidation in the respiratory chain. The electron transfer from the alcohol to molecular oxygen occurs with the aid of three coupled catalytic redox systems, leading to a low-energy pathway. An iron transfer-hydrogenation complex was utilized as a substrate-selective dehydrogenation catalyst, along with an electron-rich quinone and an oxygen-activating Co(salen)-type complex as electron-transfer mediators. Various primary and secondary alcohols were oxidized in air to the corresponding aldehydes or ketones with this method in good to excellent yields.
我们报道了首例铁催化的仿生有氧醇氧化反应。该氧化反应涉及多个电子转移步骤，这让人联想到呼吸链中的生物氧化。在三种耦合的催化氧化还原体系的辅助下，醇与分子氧之间的电子转移发生，从而形成一条低能量途径。铁转移-氢化配合物被用作底物选择性脱氢催化剂，同时使用富电子醌和氧活化的 Co(salen)型配合物作为电子转移介体。该方法可在空气中将各种伯醇和仲醇氧化为相应的醛或酮，产率良好至优秀。
