Natural Products and Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine (CSIR-IIIM), Canal Road, Jammu 180001, Jammu and Kashmir, India.
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, Uttar Pradesh, India.
J Org Chem. 2023 Feb 17;88(4):2377-2384. doi: 10.1021/acs.joc.2c02790. Epub 2023 Feb 2.
A general electrophilic iodocyclization/nucleophile addition cascade transformation for 1,2-alkynediones for the synthesis of various oxygen heterocycles and access to regioselective alkyne hydroxylation is reported. Furan-tethered ynediones resulted in the construction of -enol ethers via carbonyl-alkyne cyclization-initiated heteroarene dearomatization, whereas other (hetero)arene-, alkenyl-, and alkyl-tethered ynediones resulted in the formation of highly functionalized 3(2)-furanones. Importantly, the developed domino protocols involve the construction of important heterocyclic scaffolds and installation of two functional groups in a single operation. Moreover, the use of water as a nucleophile resulted in regioselective alkyne hydroxylation via furanone ring opening. The developed protocols are characterized by a wide substrate scope, and their utility has been demonstrated by a number of postsynthetic transformations.
报道了一种通用的亲电碘环化/亲核加成级联转化反应，用于 1,2-炔二酮的合成，可得到各种氧杂环化合物，并可实现区域选择性炔烃羟化。呋喃连接的炔二酮通过羰基-炔烃环化引发杂芳烃去芳构化反应，生成 -烯醇醚，而其他（杂）芳基、烯基和烷基连接的炔二酮则生成高度官能化的 3(2)-呋喃酮。重要的是，所开发的多步反应协议涉及重要杂环骨架的构建和两个官能团在单个操作中的安装。此外，水作为亲核试剂的使用可通过呋喃酮开环实现炔烃的区域选择性羟化。所开发的协议具有广泛的底物范围，并通过许多后合成转化证明了其有用性。
