The Institute for Drug Research, Faculty of Medicine, The Hebrew University of Jerusalem , Jerusalem 91120, Israel.
J Org Chem. 2017 Jul 21;82(14):7101-7113. doi: 10.1021/acs.joc.7b00516. Epub 2017 Jun 30.
The new reactivity of α,β-unsaturated enaminones driven by their "dual electronic attitude" is reported. We introduce unexplored, α-enaminone synthones and reveal the unusual functionalities of these building blocks. The feasibility of this new concept is demonstrated in the direct functionalization of enaminone precursors, such as alkylation; 1,2- 1,3-, or 1,4-addition; and C-O bond formation. The general and potential applicability is presented through the collective synthesis of several important classes of heterocycles via controlled cyclizations of easily accessible common precursors. The rapid composition of novel key α-enaminone synthones yields an assembly of oxazines, azaspirones, quinolinones, and quinolinols in a regio- and chemoselective fashion.
我们报道了受“双重电子态度”驱动的α，β-不饱和烯胺酮的新反应性。我们引入了尚未被探索的α-烯胺酮合成子，并揭示了这些构建块的不寻常功能。该新概念的可行性通过对烯胺酮前体的直接官能化来证明，如烷基化、1,2-、1,3-或 1,4-加成以及 C-O 键形成。通过控制容易获得的常见前体的聚合环化，集体合成几种重要类别的杂环化合物来展示其通用性和潜在适用性。新型关键α-烯胺酮合成子的快速组合以区域和化学选择性方式生成噁嗪、氮杂螺环戊烯酮、喹啉酮和喹啉醇。
