Wang Wenxiang, Pi Chao, Cui Xiuling, Wu Yangjie
Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, 450052, P. R. China.
Chemistry. 2023 May 2;29(25):e202300301. doi: 10.1002/chem.202300301. Epub 2023 Mar 20.
TBAI-catalysed [4+4]-cyclization reaction of anthranils with hydrazones to deliver oxa-bridged eight-membered heterocycles in accepted yields was developed. Preliminary mechanistic studies indicated that the reaction involved the in situ generation of vinyldiazenes from readily available hydrazones followed by an aza-Michael addition of the anthranil substrates onto the vinyldiazenes and subsequent annulation. This transformation involved the formation of two new C-N bonds and C-O bond in one pot, overcoming the synthetic limitations of anthranils in organic chemistry. This strategy benefits from high efficiency and atomic economy with mild reaction conditions.
开发了一种由四丁基碘化铵催化的邻氨基苯甲腈与腙的[4+4]环化反应，以可接受的产率得到氧桥连的八元杂环。初步机理研究表明，该反应涉及由易得的腙原位生成乙烯基重氮化合物，随后邻氨基苯甲腈底物对乙烯基重氮化合物进行氮杂迈克尔加成并随后环化。这种转化在一锅反应中形成了两个新的C-N键和C-O键，克服了有机化学中邻氨基苯甲腈的合成限制。该策略具有高效、原子经济性高以及反应条件温和的优点。
