Kang Guowei, Yamagami Masaki, Vellalath Sreekumar, Romo Daniel
Department of Chemistry and Biochemistry, Baylor University, One Bear Place #97348, Waco, TX, 76798-7348, USA.
Biomolecular Chemistry Laboratory, Department of Chemistry, Graduate School of Science, 1-1 Machikaneyama, Toyonaka, Osaka, 560-0043, Japan.
Angew Chem Int Ed Engl. 2018 May 28;57(22):6527-6531. doi: 10.1002/anie.201802483. Epub 2018 May 2.
Medium-sized lactams are important structural motifs found in a variety of bioactive compounds and natural products but are challenging to prepare, especially in optically active form. A Michael addition/proton transfer/lactamization organocascade process is described that delivers medium-sized lactams, including azepanones, benzazepinones, azocanones, and benzazocinones, in high enantiopurity through the intermediacy of chiral α,β-unsaturated acylammonium salts. An unexpected indoline synthesis was also uncovered, and the benzazocinone skeleton was transformed into other complex heterocyclic derivatives, including spiroglutarimides, isoquinolinones, and δ-lactones.
中等大小的内酰胺是多种生物活性化合物和天然产物中存在的重要结构基序，但制备起来具有挑战性，尤其是制备光学活性形式时。本文描述了一种迈克尔加成/质子转移/内酰胺化有机串联反应过程，该过程通过手性α,β-不饱和酰铵盐中间体，以高对映体纯度得到中等大小的内酰胺，包括氮杂环庚烷酮、苯并氮杂卓酮、氮杂环壬烷酮和苯并氮杂环辛酮。还发现了一种意外的吲哚啉合成方法，并且苯并氮杂环辛酮骨架被转化为其他复杂的杂环衍生物，包括螺戊二酰亚胺、异喹啉酮和δ-内酯。
