It was firstly found that the Rieke Ni generated in situ was able to promote the pinacol coupling of various carbonyls efficiently. Based on this information, another catalytically effective, cheaper and more convenient NiCl2 (Cat.)/Mg/TMSCl system was designed and developed further successfully. The interesting single-electron transfer (SET) mechanisms for the coupling reactions were proposed. Additionally, the dl/meso diastereoselectivity ...