Department of Chemistry, Faculty of Science and Technology, Keio University , 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan.
JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan.
J Org Chem. 2017 Jul 7;82(13):6503-6510. doi: 10.1021/acs.joc.6b02623. Epub 2016 Dec 29.
Ruthenium-catalyzed C-H arylation of aromatic nitriles with arylboronates is described. The use of RuH(CO){P(4-MeCH)} as a catalyst provided higher yields of the ortho arylation products than the conventional RuH(CO)(PPh) catalyst. The arylation takes place mostly at the ortho positions, but unprecedented para arylation was also partially observed to give ortho,para diarylation products. In addition to C-H bond cleavage, the cyano group was also found to function as a directing group for cleavage of C-O bonds in aryl ethers.
铑催化的芳基腈与芳基硼酸的 C-H 芳基化反应被描述。使用 RuH(CO){P(4-MeCH)}作为催化剂比传统的 RuH(CO)(PPh)催化剂提供了更高产率的邻位芳基化产物。芳基化主要发生在邻位，但也部分观察到了前所未有的对位芳基化，生成邻位、对位二芳基化产物。除了 C-H 键的断裂，氰基也被发现可以作为导向基团，断裂芳基醚中的 C-O 键。
