Gallego-Gamo Albert, Sarró Pau, Ji Yingmin, Pleixats Roser, Molins Elies, Gimbert-Suriñach Carolina, Vallribera Adelina, Granados Albert
Department of Chemistry and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Barcelona, Spain.
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, 08193 Bellaterra, Spain.
J Org Chem. 2024 Aug 16;89(16):11682-11692. doi: 10.1021/acs.joc.4c01419. Epub 2024 Aug 1.
Alkene difunctionalization is a very attractive tool in synthetic organic chemistry. Herein, we disclose an operationally and practically simple method to access 2-hydroxytrifluoroethylacetophenones from styrene derivatives via photoredox catalysis. This light-mediated transformation promotes the generation of the 1-hydroxy-2,2,2-trifluoroethyl carbon-centered radical as key synthon, which undergoes Giese addition with styrenes followed by a Kornblum oxidation process. The presented method is not only mild and cost-effective, but also utilizes an organic photocatalyst and DMSO as oxidant. Experimental investigations support the operative mechanism via net-neutral radical/polar crossover.
烯烃双官能团化是合成有机化学中一种非常有吸引力的工具。在此，我们公开了一种操作简便且实用的方法，通过光氧化还原催化从苯乙烯衍生物制备2-羟基三氟乙基苯乙酮。这种光介导的转化促进了关键合成子1-羟基-2,2,2-三氟乙基碳中心自由基的生成，该自由基与苯乙烯发生吉泽加成反应，随后进行科尔布卢姆氧化过程。所提出的方法不仅温和且具有成本效益，还使用有机光催化剂和二甲基亚砜作为氧化剂。实验研究支持了通过净中性自由基/极性交叉的操作机制。
