Department of Chemistry , University of Minnesota Twin Cities , Minneapolis , Minnesota 55455 , United States.
Org Lett. 2018 Nov 16;20(22):7253-7256. doi: 10.1021/acs.orglett.8b03168. Epub 2018 Nov 5.
The first detailed description of the catalytic racemization of activated benzylic and allylic azides under mild conditions is reported. A kinetic analysis of the observed racemization indicates a first-order dependence on azide, a first-order dependence on catalyst, and that the rate of racemization correlates to σ. A variety of azides with varying substitution patterns undergo facile racemization, and catalyst selection can tune this process.
首次详细描述了在温和条件下，活性苄基和烯丙基叠氮化物的催化外消旋化。对观察到的外消旋化的动力学分析表明，它对叠氮化物呈一级依赖，对催化剂呈一级依赖，并且外消旋化的速率与σ相关。具有不同取代模式的各种叠氮化物都可以很容易地进行外消旋化，并且可以通过选择催化剂来调节这个过程。
