Regioselective Mizoroki-Heck reactions at-position of acrylates

Mizoroki-Heck反应是最强的碳碳成键反应之一。然而，Pd催化的丙烯酸酯与芳基卤化物的Mizoroki-Heck反应产生了ORegion选择性的产物。我们考察了Pd催化的Mizoroki-Heck反应，以L的双2-萘酚为原料，合成了各种大分子配体。然而，它们的配体的体积不能控制提供区域选择性产物的足够的区域选择性。其次，合成了以吡啶甲基或吡唑基为导向基团的丙烯酰胺类化合物，目的是形成更稳定的环状中间体，使产物具有区域选择性。此外，还研究了Morita Baylis Hillman反应中产生的与烯醇中间体的芳基化反应。不幸的是，这些反应买不起想要的区域选择性产品。

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.