Puls Florian, Linke Philipp, Kataeva Olga, Knölker Hans-Joachim
Fakultät Chemie und Lebensmittelchemie, Technische Universität Dresden, Bergstrasse 66, 01069, Dresden, Germany.
A. E. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov Str. 8, Kazan, 420088, Russia.
Angew Chem Int Ed Engl. 2021 Jun 14;60(25):14083-14090. doi: 10.1002/anie.202103222. Epub 2021 May 14.
Herein, we describe a convenient and general method for the oxidation of olefins to ketones using either tris(dibenzoylmethanato)iron(III) [Fe(dbm) ] or a combination of iron(II) chloride and neocuproine (2,9-dimethyl-1,10-phenanthroline) as catalysts and phenylsilane (PhSiH ) as additive. All reactions proceed efficiently at room temperature using air as sole oxidant. This transformation has been applied to a variety of substrates, is operationally simple, proceeds under mild reaction conditions, and shows a high functional-group tolerance. The ketones are formed smoothly in up to 97 % yield and with 100 % regioselectivity, while the corresponding alcohols were observed as by-products. Labeling experiments showed that an incorporated hydrogen atom originates from the phenylsilane. The oxygen atom of the ketone as well as of the alcohol derives from the ambient atmosphere.
在此，我们描述了一种简便通用的方法，该方法使用三（二苯甲酰甲烷）铁（III）[Fe（dbm）₃]或氯化亚铁与新亚铜试剂（2,9 - 二甲基 - 1,10 - 菲咯啉）的组合作为催化剂，以苯基硅烷（PhSiH₃）作为添加剂，将烯烃氧化为酮。所有反应在室温下以空气作为唯一氧化剂高效进行。这种转化已应用于多种底物，操作简单，在温和的反应条件下进行，并且对官能团具有高耐受性。酮以高达97%的产率顺利形成，区域选择性为100%，同时观察到相应的醇作为副产物。标记实验表明，引入的氢原子源自苯基硅烷。酮以及醇的氧原子均来自周围大气。
