Study On The Asymmetric Transfer Reactions Based On Enynones As Donor And Donor-Donor Carbene Precursors

As two important carbenes,donor and donor-donor carbenes have made great progress in the past two decades.Many chemists have been attracted in this field because of the rich reactivitives and excellent reactive selectivitives of these two kinds of carbenes.In recent years,as an important non-diazo donor and donor-donor carbene sources,enynones involved reactions have been attracted more and more attention.Compared to diazo-type compounds as donor and donor-donor carbene precursors,enynones have the following obvious advantages:1.The reactions have no risk of explosion;2.This kind of carbene source has low toxicity;3.The reactions can be conducted in one-pot manner and no requirement for the slow addition;4.The reaction atom efficiency can be up to 100% and the reactions can be easily scaled up.This paper was systematically studied enynones used as carbene precursors based on the past research background in our group.Their chemical transformations of high chemoselectivitives and enantioselectivitives with donor and donor-donor metal carbenes as intermediates were explored under transition-metal catalytic conditions.This paper was structured in four parts as follows:The first section introduced the methods of the formation of donor and donor-donor carbenes and recent advances of chemical transformation with these carbene species as intermediates.As the carbene source,enynones as well as their carbene tranfer reactions were introduced in detail.The second section studied that the high chemoselectivity and stereoselectivity of intramolecular allyl C-H insertion and propanation can be realized when the allyl enynones used as carbene precursors,under the ruthenium and chiral pyridine-Box ligands catalytic system and chiral rhodium carboxylate dimer catalytic conditions respectively.When the alkyl substituted enynones were used as carbene precursors,the high disenantioselective and enantioselective intramolecular alkyl C-H insertion was occurred under the ruthenium and chiral pyridine-Box ligands catalytic system.The third section studied that the imtramolecular Buchner reaction was occurred when the o-aryl ether substituted enynones were used as carbene precursors under chiral rhodium carboxylate dimer catalytic conditions.This reaction could synthesize a seires of high enantioselective polycyclic products under mild conditions.Moreover,with the in-depth control experiments,the mechanism of gradually racemization of chiral Buchner products were clarified.The fourth section studied that the imtramolecular aryl substitution reaction was occurred when the o-aryl substituted enynones were used as carbene precursors.A seires of furan substituted chiral fluorene derivatives were synthesized through this reaction.This reaction showed high siteselectivity and high enantioselectivity.