Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai 200438, P. R. China.
Department of Oncology, Shanghai Medical College, Fudan University, Shanghai 200032, P. R. China.
J Org Chem. 2023 Feb 17;88(4):2521-2534. doi: 10.1021/acs.joc.2c02976. Epub 2023 Jan 26.
A visible light-induced diastereoselective synthesis of trifluoromethylated cyclobutane derivatives is described, consisting of [2+2]-photocycloaddition and water-assisted hydrodebromination by one pot. Quinolinones, isoquinolinones, and coumarins are able to participate in this one-pot process with 1-bromo-1-trifluoromethylethene. In addition, stereodefined trisubstituted trifluoromethylated cyclobutane alcohols, carboxylic acids, and amines can be obtained in a straightforward manner through the ring opening of lactone or lactam without the loss of original high diastereoselectivity given by the water-tristrimethylsilylsilane coordination. The antineoplastic bioactivities of those compounds are also well studied, which exhibit great antineoplastic potential comparable to cisplatin. In the proposed mechanism, thioxanthone (TX) serves as a dual catalyst and a radical chain pathway may be involved in the hydrodebromination process.
可见光诱导的手性选择性合成三氟甲基化环丁烷衍生物的方法，包括一锅法的[2+2]-光环加成和水辅助氢脱溴。喹啉酮、异喹啉酮和香豆素能够与 1-溴-1-三氟乙 烯一起参与这一锅反应。此外，通过内酯或内酰胺开环，可以以直接的方式获得立体定义的三取代三氟甲基化环丁烷醇、羧酸和胺，而不会失去水-三（三甲基甲硅烷基）硅烷配位所赋予的原始高对映选择性。这些化合物的抗肿瘤生物活性也得到了很好的研究，它们表现出与顺铂相当的巨大抗肿瘤潜力。在提出的机制中，噻吨酮 (TX) 作为双催化剂，氢脱溴过程可能涉及自由基链途径。
