Ligand‐Promoted Rh I ‐Catalyzed C2‐Selective C−H Alkenylation and Polyenylation of Imidazoles with Alkenyl Carboxylic Acids
Ligand‐Promoted Rh I ‐Catalyzed C2‐Selective C−H Alkenylation and Polyenylation of Imidazoles with Alkenyl Carboxylic Acids
复制标题
配体-促进Rh I-催化C2-选择性C-H烯基化和咪唑与烯基羧酸的多烯化
DOI：
10.1002/chem.202200441
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Walsh, Patrick J.
中科院分区：
文献类型：
--
作者：
Zhao, Haoqiang;Luo, Zhenli;Yang, Ji;Li, Bohan;Han, Jiahong;Xu, Lijin;Lai, Wenzhen;Walsh, Patrick J.
报道了第一个RhI催化的咪唑与易得的烯基羧酸的定向脱羰化C2 - H烷基化反应。该反应以高度区域选择性和立体选择性的方式进行，提供了通过已知的C - H烯化方法通常无法获得的C2 -烯化咪唑的有效途径。这种转化适应广泛的烯基羧酸，包括具有挑战性的共轭多烯羧酸，以及具有高官能团相容性的各种修饰咪唑。可移动嘧啶导向基团的存在和双齿膦配体的使用是催化反应成功的关键。该工艺也适用于苯并咪唑。重要的是，产品的可扩展性和多样性突出了该协议在实际应用中的潜力。详细的实验和计算研究为潜在的反应机制提供了重要的见解。
The first RhI‐catalyzed, directed decarbonylative C2−H alkenylation of imidazoles with readily available alkenyl carboxylic acids is reported. The reaction proceeds in a highly regio‐ and stereoselective manner, providing efficient access to C2‐alkenylated imidazoles that are generally inaccessible by known C−H alkenylation methods. This transformation accommodates a wide range of alkenyl carboxylic acids, including challenging conjugated polyene carboxylic acids, and diversely decorated imidazoles with high functional group compatibility. The presence of a removable pyrimidine directing group and the use of a bidentate phosphine ligand are pivotal to the success of the catalytic reaction. This process is also suitable for benzimidazoles. Importantly, the scalability and diversification of the products highlight the potential of this protocol in practical applications. Detailed experimental and computational studies provide important insights into the underlying reaction mechanism.