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反应是最强的碳碳成键反应之一。然而，钯催化的Mizoroki-Heck反应的丙烯酸酯与芳基卤得到oregioselectivity产品。本文研究了以1，1 '-联2-萘酚为原料，在各种大体积配体存在下，Pd催化的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，得到区域选择性产物。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，旨在形成更稳定的钯化合物中间体，从而产生区域选择性产物。此外，还研究了Morita Baylis Hillman反应中烯醇化中间体的芳基化反应。不幸的是，这些反应没有得到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: 清田祐基;濱松真由;入江亮;嶋田豊司
• 通讯作者: 嶋田豊司