Millimaci Alexandra M, Knirsch Antonin C, Beeler Aaron B
Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States.
Org Lett. 2024 Sep 13;26(36):7484-7488. doi: 10.1021/acs.orglett.4c02126. Epub 2024 Sep 4.
A photoredox catalyzed [3 + 2] dipolar cycloaddition between acyclic carbonyl ylides generated from α-cyano epoxides and dipolarophiles is described. This method, influenced by anionic charge localization and temperature control, enabled the synthesis of regioselective functionalized cyclic ethers. By leveraging different dipolarophiles, Lewis acid mediated activation afforded either furan or hydroxy-dihydronaphthalene scaffolds. A direct synthesis of lignan natural products isodiphyllin and diphyllin is achieved by exploiting the nitrile's reactivity as a directing handle for the desired regioisomer.
本文描述了一种光氧化还原催化的[3+2]偶极环加成反应，该反应发生在由α-氰基环氧化物生成的无环羰基叶立德与亲偶极体之间。受阴离子电荷定位和温度控制的影响，该方法能够合成区域选择性官能化的环状醚。通过利用不同的亲偶极体，路易斯酸介导的活化作用可得到呋喃或羟基二氢萘骨架。通过利用腈作为所需区域异构体的导向基团的反应活性，实现了木脂素天然产物异二叶豆素和二叶豆素的直接合成。
