过硫酸盐促进质子化脂肪族伯胺的远程 C(sp3)-H 氧代反应。
Remote C(sp)-H Oxygenation of Protonated Aliphatic Amines with Potassium Persulfate.
机构信息
University of Michigan , Department of Chemistry, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
出版信息
Org Lett. 2017 Feb 3;19(3):572-575. doi: 10.1021/acs.orglett.6b03731. Epub 2017 Jan 17.
Abstract
This letter describes the development of a method for selective remote C(sp)-H oxygenation of protonated aliphatic amines using aqueous potassium persulfate. Protonation serves to deactivate the proximal C(sp)-H bonds of the amine substrates and also renders the amines soluble in the aqueous medium. These reactions proceed under relatively mild conditions (within 2 h at 80 °C with amine as limiting reagent) and do not require a transition metal catalyst. This method is applicable to a variety of types of C(sp)-H bonds, including 3°, 2°, and benzylic C-H sites in primary, secondary, and tertiary amine substrates.
摘要
这封信描述了一种使用过硫酸钾选择性远程 C(sp)-H 氧化质子化脂肪族胺的方法的开发。质子化作用可使胺底物的近侧 C(sp)-H 键失活，并且还使胺在水相介质中可溶。这些反应在相对温和的条件下进行（在 80°C 下，以胺为限制试剂，在 2 小时内进行），并且不需要过渡金属催化剂。该方法适用于多种类型的 C(sp)-H 键，包括伯、仲和叔胺底物中 3°、2°和苄基 C-H 位。
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