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Trifluoromethylation of Metal Enolates and Theoretical Guideline

机译：金属烯醇盐的三氟甲基化及其理论指导

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摘要

The difficulty as well as the significance of the direct generation of metal enolates of α-CF_3-ketones cannot be easily understood by chemists unfamiliar with fluorine. In sharp contrast to the great success in non-fluorine, hydrocarbon chemistry, fluorine chemistry has long been overshadowed. Metal enolates of carbonyl compounds are synthetically important in carbon-carbon bond forming reactions. However, the metal enolates of fluorinated carbonyl compounds have been severely limited to α-F metal enolates. α-CF_3 Metal enolates have generally been recognized as unstable and difficult to prepare because of the facile β-M-F elimination. However, we have developed a direct generation and synthetic application of α-CF_3 metal enolates. Therefore, the present results regarding the direct generation and synthetic use of metal enolates of α-CF_3-ketones might be recognized as a paradigm shift to the general use of metal enolates in fluorine chemistry.
机译：不熟悉氟的化学家不容易理解直接生成α-CF_3-酮的金属烯醇化物的困难及其意义。与在非氟碳氢化合物化学领域取得的巨大成功形成鲜明对比的是，氟化学早已被人们所忽略。羰基化合物的金属烯醇化物在碳-碳键形成反应中具有重要的合成作用。然而，氟化羰基化合物的金属烯醇化物已被严格地限于α-F金属烯醇化物。由于容易消除β-M-F，α-CF_3金属烯酸酯通常被认为是不稳定的且难以制备。然而，我们已经开发了α-CF_3金属烯醇化物的直接生成和合成应用。因此，关于α-CF_3-酮的金属烯醇化物的直接产生和合成用途的当前结果可能被认为是氟化学中金属烯醇化物的普遍使用的范式转变。

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