Regioselective Mizoroki-Heck reactions at-position of acrylates

丙烯酸酯位点区域选择性 Mizoroki-Heck 反应

• 批准号: 21550108
• 负责人: SHIMADA Toyoshi
• 金额: $ 2.91万
• 依托单位: Nara National College of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2009
• 资助国家: 日本
• 起止时间: 2009 至 2011
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21550108/
• 关键词: 選択的合成; 反応; 溝呂木・ヘック反応; 位置選択性; パラジウム触媒; ホスフィン配位子; α位

Mizoroki-Heck reaction is one of the most powerful carboncarbon bondforming reactions. However, Pdcatalyzed Mizoroki-Heck reactions of acrylates with aryl halides give oregioselective products. We examined Pdcatalyzed Mizoroki-Heck reaction in the presence of various bulky ligands, prepared from 1, l' bi2naphthol. Bulkiness of their ligands, however, could not control the sufficient regioselectivity giving aregioselective product. Next, acrylic amides having pyridylmethyl or pyrazolyl group as directing group were prepared, aiming to form more stable palladacycle intermediate leading to aregioselective product. In addition, arylation with enolate intermediate generated during Morita Baylis Hillman reaction was investigated. Unfortunately, these reactions did not afford the desired aregioselective product.

Mizoroki-Heck 反应是最强大的碳碳键形成反应之一。然而，丙烯酸酯与芳基卤化物的 Pdc 催化 Mizoroki-Heck 反应产生了区域选择性产物。我们检查了在由 1, 1' 联萘酚制备的各种大配体存在下的 Pdc 催化 Mizoroki-Heck 反应。然而，它们的配体的体积不能控制足够的区域选择性，从而产生区域选择性产物。接下来，制备具有吡啶基甲基或吡唑基作为导向基团的丙烯酰胺，旨在形成更稳定的环环中间体，从而产生区域选择性产物。此外，还研究了 Morita Baylis Hillman 反应过程中产生的烯醇化物中间体的芳基化。不幸的是，这些反应没有提供所需的区域选择性产物。

项目成果

月刊ファインケミカル12

精细化工月刊12

• 发表时间: 2010
• 作者: 嶋田豊司