Malkova Ksenia, Tatarinov Ilya, Kantin Grigory, Dar'in Dmitry
Saint Petersburg State University, Saint Petersburg 199034, Russian Federation.
Saint Petersburg Research Institute of Phthisiopulmonology, Saint Petersburg 191036, Russian Federation.
J Org Chem. 2024 Feb 16;89(4):2782-2786. doi: 10.1021/acs.joc.3c02474. Epub 2024 Feb 1.
Herein, we report a novel approach for the assembly of spirocyclic Δ-butenolides and β-methylidene 2-furanones via Rh(II)-catalyzed O-H insertion of heterocyclic diazo compounds into allenic acids followed by base-promoted cyclization. Utilizing various diazo heterocycles, including α-diazo homophthalimides, 3-diazo tetramic acids, and diazo oxindoles, diverse spirocyclic scaffolds were produced. The research revealed that the allenic acid substitution pattern is decisive for the product type, enabling extraordinary target compound switching between two types of spirocyclic 2-furanones with exo- and endocyclic C═C bonds.
在此，我们报道了一种通过铑（II）催化的杂环重氮化合物与联烯酸的O-H插入反应，随后进行碱促进的环化反应来组装螺环Δ-丁烯内酯和β-亚甲基-2-呋喃酮的新方法。利用各种重氮杂环化合物，包括α-重氮邻苯二甲酰亚胺、3-重氮四胺酸和重氮氧化吲哚，制备了多种螺环骨架。研究表明，联烯酸的取代模式对产物类型起决定性作用，能够在具有外环和内环C═C键的两种螺环2-呋喃酮之间实现非凡的目标化合物转换。
