Regioselective Mizoroki-Heck reactions at-position of acrylates

Mizoroki-Heck反应是最强大的碳-碳成键反应之一。然而，钯催化的丙烯酸酯与芳基卤化物的Mizoroki-Heck反应产生了选择性产物。我们研究了pd1催化的Mizoroki-Heck反应在各种大体积配体的存在下，由1,1 ' bi2naphthol制备。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。其次，制备了以吡啶甲基或吡唑基为导向基团的丙烯酸酰胺，旨在形成更稳定的钯环中间体，从而产生区域选择性产品。此外，对Morita Baylis Hillman反应中产生的烯酸酯中间体的芳基化反应进行了研究。不幸的是，这些反应不能产生期望的区域选择性产物。

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.