Maity Anirban, Studer Armido
Organisch-Chemisches Institut, Universität Münster, 48149 Münster, Germany.
Org Lett. 2024 Jun 7;26(22):4784-4787. doi: 10.1021/acs.orglett.4c01607. Epub 2024 May 30.
An intramolecular 1,2-amidooxygenation of unactivated alkenes for the construction of the pyrrolidinone scaffold containing a masked 5-hydroxymethyl functionality is reported. γ,δ-Unsaturated -aryloxyamides react with sodium 2,2,6,6-tetramethylpiperidin-1-olate (TEMPONa) to afford alkoxyaminated pyrrolidinones. The cascade proceeds through reductive amidyl radical generation with TEMPONa, 5-exo cyclization, and TEMPO trapping. No transition metal is required to perform these transformations, and complex (fused, bridged) pyrrolidinones are accessible in moderate to good yields. The product alkoxyamines are readily further converted into ketones and alcohols through either oxidation or reduction.
报道了一种用于构建含有掩蔽的5-羟甲基官能团的吡咯烷酮支架的未活化烯烃的分子内1,2-酰胺基氧化反应。γ,δ-不饱和芳氧基酰胺与2,2,6,6-四甲基哌啶-1-醇钠（TEMPONa）反应，得到烷氧基胺化的吡咯烷酮。该串联反应通过用TEMPONa生成还原酰胺基自由基、5-外向环化和TEMPO捕获来进行。进行这些转化不需要过渡金属，并且可以以中等至良好的产率获得复杂（稠合、桥连）的吡咯烷酮。产物烷氧基胺很容易通过氧化或还原进一步转化为酮和醇。
