Synthesis of Group 4 Metal Complexes Stabilized by an Amine-Bridged Bis(phenolato) Ligand and Their Catalytic Behavior in Intermolecular Hydroamination Reactions
Qiu Sun †, Yaorong Wang †, Dan Yuan *†,(袁丹) Yingming Yao *†‡,（姚英明） and Qi Shen †
† Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Dushu Lake Campus, Suzhou 215123, People’s Republic of China
‡ The Institute of Low Carbon Economy, Suzhou 215123, People’s Republic of China
Organometallics 2014, 33, 994–1001
Zirconium and titanium complexes 1 and 2, bearing an amine-bridged bis(phenolato) ligand, have been synthesized and characterized. Although 1 and 2 were inactive in catalyzing intermolecular hydroamination reactions, cationic complexes generated in situ from treatment of 1 and 2 with borate [Ph3C][B(C6F5)4], respectively, were found to be highly active. In general, excellent yields (up to >99%) and 100% regioselectivity for a broad range of terminal alkynes and anilines were observed within a reaction time of 1 h. Reactions with internal alkynes of moderate sterics also led to good yields and moderate regioselectivity. A kinetic study was also conducted, which provided some insights into the mechanism of hydroamination reactions.
链接： //pubs.acs.org/doi/abs/10.1021/om401158a
