Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India.
J Org Chem. 2023 May 5;88(9):5652-5660. doi: 10.1021/acs.joc.3c00141. Epub 2023 Apr 17.
Metal- and additive-free, photoinduced decarboxylative radical alkylation-cyclization of CF-acrylamides with alkyl redox-active esters provided the corresponding quaternary CF-oxindole derivatives in good yields. Notably, diaryliodonium salts also efficiently participated in the arylation-cyclization of CF-acrylamides in environmentally benign HO as a solvent. The present approach has been extended for the concise synthesis of CF-attached indoline alkaloid analogues, i.e., CF-(±)-desoxyeseroline, CF-(±)-esermethole, and CF-(±) progesterone receptor antagonists. The preliminary mechanistic studies revealed that the reaction is likely to proceed through initial photoexcitation of redox-active ester/diaryliodonium salts followed by the SET process with acrylamide.
无金属和添加剂、光诱导的 CF-丙烯酰胺与烷基氧化还原活性酯的脱羧基自由基烷基化-环化反应以良好的收率提供了相应的季 CF-氧吲哚衍生物。值得注意的是，二芳基碘𬭩盐也能有效地作为溶剂在环境友好的 HO 中参与 CF-丙烯酰胺的芳基环化反应。本方法已扩展用于简洁合成 CF 连接的吲哚生物碱类似物，即 CF-(±)-去氧依索林、CF-(±)-表美托龙和 CF-(±)孕激素受体拮抗剂。初步的机理研究表明，反应可能通过氧化还原活性酯/二芳基碘𬭩盐的初始光激发，然后与丙烯酰胺进行 SET 过程来进行。
