Studies On The Cu(?)-Catalyzed Carbometallation Of Oxabiyclic Olefins

The ring-opening cross coupling reaction of oxabicyclic olefin is a significant process in organometallic chemistry which allows facile construction of functionalized benzocarbocycles with C-C bond construction.The product benzocarbocycle is also present in a variety of bioactive and pharmaceutical molecules.The reaction has been intensively studied and many transition metals were found to promote this process.A survey of literature has revealed that the practicality of this process has been limited to employing either coupling functional group-tolerant carbon sources such as organoboronic reagents with precious metal catalysts,or using base metal catalysts with strongly basic Grignard or organozinc reagents as carbon source.Processes featuring both base-metal catalysis and FG-tolerant carbon sources are scare.This thesis is aimed toward developing such a process as mentioned above.We have developed a Cu(?)-catalyzed ring-opening cross-coupling reaction of oxabicyclic olefin with organoboronic ester as carbon sources.The reaction has demonstrated high functional group tolerance and could proceed under mild conditions,delivering products with complementary stereochemistry compared to related reaction with organozinc as carbon souces.Preliminary catalytic asymmetric studies have also been examined.This study represents a valuable addition to the relatively reservoir of Cu(?)-catalyzed carbometallation with organoboronic reagents.