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Chemoselective Ketone Synthesis by the Strontium‐mediated Alkylation or Arylation of N,N‐Dimethylamides or Urea
Asian Journal of Organic Chemistry ( IF 2.7 ) Pub Date : 2020-08-16 , DOI: 10.1002/ajoc.202000389 Norikazu Miyoshi 1, 2 , Shodai Kimura 2 , Shigeki Kubo 2 , Satoshi D. Ohmura 1, 2, 3 , Masaharu Ueno 1, 2
Asian Journal of Organic Chemistry ( IF 2.7 ) Pub Date : 2020-08-16 , DOI: 10.1002/ajoc.202000389 Norikazu Miyoshi 1, 2 , Shodai Kimura 2 , Shigeki Kubo 2 , Satoshi D. Ohmura 1, 2, 3 , Masaharu Ueno 1, 2
Affiliation
Ketone synthesis via the addition of organometallic reagents to amides has long been investigated. In many cases, it is necessary to control the solvent, reaction temperature, and adhere to strict nucleophile stoichiometry for each combination of amide and organometallic reagent. Strontium, with an electronegativity comparable to lithium but a larger ionic radius, may display high reactivity with the characteristics of monoalkylation. Here, we show that the monoalkylation of various N,N‐dimethylamide derivatives with alkyl iodides to afford the ketones proceeds smoothly under generally mild temperature conditions. By this method, not only aromatic amides but also α‐proton‐bearing aliphatic amides were suitable substrates for ketone synthesis. In addition, we found that tetramethylurea, typically a poor electrophile, also reacted to afford benzophenone in good yield with excellent selectivity.
中文翻译:
N,N-二甲基酰胺或尿素的锶介导的烷基化或芳基化反应合成化学选择性酮
长期以来一直在研究通过将有机金属试剂添加到酰胺中来合成酮。在许多情况下,对于酰胺和有机金属试剂的每种组合,必须控制溶剂,反应温度并遵守严格的亲核化学计量。具有与锂相当的电负性,但离子半径较大的锶,可能会显示出具有单烷基化特征的高反应性。在这里,我们表明各种N,N的单烷基化带有烷基碘的二甲基酰胺衍生物可提供酮,通常在温和的温度条件下可顺利进行。通过这种方法,不仅芳香酰胺,而且α-质子载脂族酰胺都是适合酮合成的底物。另外,我们发现通常为弱亲电试剂的四甲基脲也反应生成苯甲酮,收率高,选择性好。
更新日期:2020-10-11
中文翻译:
N,N-二甲基酰胺或尿素的锶介导的烷基化或芳基化反应合成化学选择性酮
长期以来一直在研究通过将有机金属试剂添加到酰胺中来合成酮。在许多情况下,对于酰胺和有机金属试剂的每种组合,必须控制溶剂,反应温度并遵守严格的亲核化学计量。具有与锂相当的电负性,但离子半径较大的锶,可能会显示出具有单烷基化特征的高反应性。在这里,我们表明各种N,N的单烷基化带有烷基碘的二甲基酰胺衍生物可提供酮,通常在温和的温度条件下可顺利进行。通过这种方法,不仅芳香酰胺,而且α-质子载脂族酰胺都是适合酮合成的底物。另外,我们发现通常为弱亲电试剂的四甲基脲也反应生成苯甲酮,收率高,选择性好。