Jamshidi Elmira, Rajai-Daryasarei Saideh, Stranger Robert, Ariafard Alireza, Rominger Frank, Balalaie Saeed
Peptide Chemistry Research Institute, K. N. Toosi University of Technology, P.O. Box 15875-4416, Tehran, 19697, Iran.
Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.
Chemistry. 2025 Jun 23;31(35):e202501015. doi: 10.1002/chem.202501015. Epub 2025 Jun 3.
1-Indanone derivatives are efficiently synthesized via a radical cyclization reaction of 1,6-enynes, using TBHP as both oxidant and reactant, in the presence of Cu(I) as the catalyst and 4-methyl benzoic acid as the cocatalyst. Notably, in the absence of 4-methyl benzoic acid, the reaction undergoes a dramatic shift in product selectivity, yielding 1H‑cyclopropa[b]naphthalene-2,7-diones exclusively under the same conditions, with Cu(I) acting as the sole catalyst. This transformation offers key advantages, including operational simplicity, cost-effective and readily available materials, scalability to gram quantities, and compatibility with a wide range of functional groups. Mechanistic studies and DFT calculations confirmed that the reaction proceeds through a radical pathway, highlighting the pivotal role of 4-methylbenzoic acid as the cocatalyst in altering product selectivity.
通过1,6-烯炔的自由基环化反应，以叔丁基过氧化氢（TBHP）作为氧化剂和反应物，在铜（I）作为催化剂和4-甲基苯甲酸作为助催化剂的存在下，高效合成了1-茚酮衍生物。值得注意的是，在没有4-甲基苯甲酸的情况下，反应的产物选择性发生了显著变化，在相同条件下仅生成1H-环丙烷并[b]萘-2,7-二酮，铜（I）作为唯一的催化剂。这种转化具有关键优势，包括操作简单、材料经济实惠且易于获得、可扩展至克级规模以及与多种官能团兼容。机理研究和密度泛函理论（DFT）计算证实该反应通过自由基途径进行，突出了4-甲基苯甲酸作为助催化剂在改变产物选择性方面的关键作用。
