Cross-Coupling of Aryl/Alkenyl Ethers with Aryl Grignard Reagents through Nickel-Catalyzed CO Activation
作者:Lan-Gui Xie、Zhong-Xia Wang
DOI:10.1002/chem.201003731
日期:2011.4.26
achieved through the cleavage of the sp2 CO bond of aryl/alkenyl ethers catalyzed by a nickel complex, and by using Grignard reagents as nucleophiles (see scheme). This method displays a broad substrate scope and leads to good to excellent yields of the aryl–aryl or alkenyl–aryl cross‐coupling products.
remains challenging. Herein, a protocol for Rh(II)-catalyzed and CO2-involved carboxylation of inert sp2 C–H bonds from the cyclopentadienyl (Cp) ring of ferrocene derivatives was reported, which produces a series of ferrocene-embedded lactones that are important molecular skeletons widely used in pharmaceuticals or ligands. Moreover, moderate enantioselectivity was achieved with a chiral NHC ligand, which
二氧化碳 (CO 2 ) 被认为是绿色和可再生的 C1 原料。然而,由于其热力学和动力学稳定性,过渡金属催化未活化的 C-H 键与 CO 2的羧化反应仍然具有挑战性。在此,报道了 Rh( II ) 催化和 CO 2参与的二茂铁衍生物环戊二烯基 (Cp) 环惰性 sp 2 C-H 键羧化反应的方案,该方案产生了一系列重要的二茂铁嵌入内酯广泛用于药物或配体的分子骨架。此外,使用手性 NHC 配体实现了适度的对映选择性,这可以被视为与 CO 2进行不对称 C-H 羧化的第一个例子. 初步的机理实验支持二价铑作为真正的活性催化剂,并据此提出了合理的催化循环。