Rychnovsky S D, Hata T, Kim A I, Buckmelter A J
Department of Chemistry, 516 Rowland Hall, University of California, Irvine, California 92697-2025, USA.
Org Lett. 2001 Mar 22;3(6):807-10. doi: 10.1021/ol006866r.
The reductive lithiation of nitrile 9 led to the cyclic product 11 as a single diastereomer in 42% ee. The intermediate radical is a conformational radical clock. The radical lifetime can be determined from the optical purity of the product 11. We show that the lifetime of the intermediate radical is too brief to allow a radical cyclization, and thus the cyclization proceeds through an alkyllithium intermediate.
腈9的还原锂化反应生成了环状产物11，其为单一非对映异构体，对映体过量为42%。中间体自由基是一个构象自由基时钟。自由基寿命可由产物11的光学纯度确定。我们表明，中间体自由基的寿命过短，无法发生自由基环化反应，因此环化反应是通过烷基锂中间体进行的。
