碘化亚铜介导Reformatsky反应高效合成β-羟基酯

CuI mediated efficient synthesis of β-Hydroxy esters by the reformatsky reaction

摘要:

发展了一种由碘化亚铜介导的简易高效的Reformatsky催化体系。在便宜易得碘化亚铜的介导下，实现了锌粉高效催化碘代乙酸乙酯2a与芳醛1/酮3的Reformatsky反应。以乙腈/水混合溶剂为反应溶剂，温和条件下高收率地合成了32个β-羟基酯类I~XXXII(产率82%~95%)。产物结构经1 HNMR、13 CNMR和MS 确证。依据前期研究及相关文献，提出了可能的反应机理。此外，该催化方法学还可放大至克级规模，以10 mmol苯甲醛1a、15 mmol碘代乙酸乙酯2a为原料，高产率地获得了β-羟基酯I (1.94 g，92%)。

Abstract:

A simple and efficientcuprous iodide-mediated catalytic system of reformatsky reaction has been described. The reformatsky reaction of ethyl iodoacetate2a with aromatic aldehydes 1/ketones3 was efficiently catalyzed by zinc powder and mediated by the cheap and easily available cuprous iodide. With acetonitrile/water mixed solvent as the reaction solvent, 32 β-hydroxyl esters I~XXXII were synthesizedwith high yield (82%~95% yield) under mild conditions. The structures of products obtained were confirmed by 1 HNMR, 13 CNMR and MS. According to the previous research and the related literature, the possible reaction mechanism was proposed. In addition, the catalytic methodology can be scaled up to the gram scale.With benzaldehyde 1a (10 mmol) and ethyl iodoacetate 2a (15 mmol) as raw materials, β-hydroxyl ester I (1.94 g, yield 92%) was obtained from with high yield.