A General and Special Catalyst for Suzuki–Miyaura Coupling.pdfVIP

Angewandte Chemie DOI: 10.1002/anie.座机电话号码4 Cross-Coupling A General and Special Catalyst for Suzuki–Miyaura Coupling Processes Wenjun Tang,* Andrew G. Capacci, Xudong Wei, Wenjie Li, Andre White, Nitinchandra D. Patel, Jolaine Savoie, Joe J. Gao, Sonia Rodriguez, Bo Qu, Nizar Haddad, Bruce Z. Lu, Dhileepkumar Krishnamurthy, Nathan K. Yee, and Chris H. Senanayake Since its discovery,[1] the Suzuki–Miyaura cross-coupling phosphorus ligands 1a–d whose structures feature a 2,3- reaction has evolved into one of most powerful carbon dihydrobenzo[d][1,3]oxaphosphole framework Figure 1 . carbon bond-forming transformations and has shown increas- Unlike SPhos where the dicyclohexylphosphanyl group can ing utility in synthetic organic chemistry.[2] Recent advances in novel catalyst development[3] have enabled this transforma- tion to be applied with a broad substrate scope, a wide functional group tolerance, and low catalyst loadings. Palla- dium catalysts derived from electron-rich and sterically demanding ligands, such as trialkyl monophosphanes,[4] di- alkyl aryl monophosphanes,[5] dialkyl biaryl monophos- phanes,[6] N-heterocyclic carbenes,[7] and other ligands,[8] have been particularly effective. Despite these advances, limitations remain. For example, the Suzuki–Miyaura cou- pling of extremely hindered arylboronic acids, such as 2,4,6- Figure 1. Biaryl monophosphorus ligands. triisopropylphenylboronic acid have been less explored. Few successful results have been reported for the preparation of tri-ortho-substituted biaryls from such extremely hindered freely rotate along the upper aryl ring and multiple con- boronic acids. The development of novel, efficient, and formers are present when coordinating with a metal center,[12] general catalysts for the Suzuki–Miyaura cross-coupling the structures