Neal Edward A, Goldup Stephen M
School of Biological and Chemical Sciences , Queen Mary University of London , Mile End Road , London , E1 4NS , UK.
Department of Chemistry , University of Southampton , Highfield , Southampton , Hampshire SO17 1BJ , UK . Email:
Chem Sci. 2015 Apr 1;6(4):2398-2404. doi: 10.1039/c4sc03999h. Epub 2015 Feb 3.
We recently identified competitive formation of doubly interlocked [3]rotaxanes as the origin of the non-linear variation in yield of [2]rotaxane with macrocycle size in the bipyridine-mediated AT-CuAAC reaction. Selection of reaction conditions gave [2]rotaxanes in essentially quantitative yield in all cases and hard to access doubly threaded [3]rotaxanes in up to 50% yield in a single, four component coupling. Based on the effect of macrocycle structure on the reaction outcome we propose a detailed mechanism of [3]rotaxane formation.
我们最近发现，在联吡啶介导的AT-CuAAC反应中，双互锁[3]轮烷的竞争性形成是[2]轮烷产率随大环尺寸呈非线性变化的原因。通过选择反应条件，在所有情况下均可获得基本定量产率的[2]轮烷，并且在单一的四组分偶联反应中，以高达50%的产率获得难以制备的双股[3]轮烷。基于大环结构对反应结果的影响，我们提出了[3]轮烷形成的详细机制。
