Department of Chemistry & Biochemistry, University of California , Santa Barbara, California 93106, United States.
Org Lett. 2015 Sep 18;17(18):4514-7. doi: 10.1021/acs.orglett.5b02208. Epub 2015 Aug 28.
The first example of a general asymmetric nitrosocarbonyl hetero-ene reaction is described. The procedure uses a copper-catalyzed aerobic oxidation of a commercially available chiral nitrosocarbonyl precursor (EleNOr) and is operationally simple. The transformation is both high yielding and highly diastereoselective for a range of silyl enol ether derivatives. A variety of synthetically useful postfunctionalization reactions are presented along with a mechanistic rationale that can be used as a predictive model for future asymmetric reactions with nitrosocarbonyl intermediates.
首次描述了一种通用的不对称硝酰基杂烯反应实例。该方法采用铜催化的商业可得手性硝酰基前体（EleNOr）的有氧氧化，操作简单。该转化具有高产率和高非对映选择性，适用于一系列硅基烯醇醚衍生物。还提出了各种具有合成用途的后官能化反应以及一个可以用作未来硝酰基中间体不对称反应的预测模型的机理理由。
