普林斯环化反应中的外消旋化
Racemization in Prins cyclization reactions.
作者信息
Jasti Ramesh, Rychnovsky Scott D
机构信息
Department of Chemistry, University of California-Irvine, 1102 Natural Sciences II, Irvine, CA 92697-2025, USA.
出版信息
J Am Chem Soc. 2006 Oct 18;128(41):13640-8. doi: 10.1021/ja064783l.
Abstract
Isotopic labeling experiments were performed to elucidate a new mechanism for racemization in Prins cyclization reactions. The loss in optical activity for these reactions was shown to occur by 2-oxonia-Cope rearrangements by way of a (Z)-oxocarbenium ion intermediate. Reaction conditions such as solvent, temperature, and the nucleophile employed played a critical role in whether an erosion in enantiomeric excess was observed. Additionally, certain structural features of Prins cyclization precursors were also shown to be important for preserving optical purity in these reactions.
摘要
进行了同位素标记实验，以阐明普林斯环化反应中消旋化的新机制。这些反应中旋光活性的丧失被证明是通过（Z）-氧鎓离子中间体经2-氧杂环丁烷-科普重排发生的。诸如溶剂、温度和所用亲核试剂等反应条件，对于是否观察到对映体过量的降低起着关键作用。此外，普林斯环化前体的某些结构特征对于在这些反应中保持光学纯度也很重要。
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