Copper(Ⅰ)-Catalyzed Asymmetric Construction Of Tetrasubstituted Carbon Centers

This dissertation mainly focused on:(1)asymmetric construction of tetrasubstituted carbon centers by copper(I)-catalyzed borylative aldol reaction;(2)Asymmetric construction of tetrasubstituted non-gem-diboronated stereogenic carbon centers by copper(I)-catalyzed conjugate boration.(1)Asymmetric construction of tetrasubstituted carbon centers bycopper(Ⅰ)-catalyzed borylative aldol reaction.A copper(Ⅰ)-catalyzed asymmetric borylative aldol reaction of 5,6-dihydro-2H-pyran-2-one and simple ketones(including aromatic ketones and a aliphatic ketone)was disclosed,which afforded a series of chiral diols after an oxidative work-up in moderate yields with moderate to high diastereoselectivity and excellent enantioselectivity.The lactone moiety was easily opened with methanol to generate a chiral triol in moderate yield.(2)Asymmetric construction of tetrasubstituted non-gem-diboronatedstereogenic carbon centers by copper(I)-catalyzed conjugate boration.A copper(Ⅰ)-catalyzed asymmetric conjugate boration of(E)-β-Bdan-β-substituted α,β-unsaturated esters was disclosed,which afforded a series chiral tetrasubstituted non-gem-diboronated stereogenic carbon centers in good to excellent yields with excellent enantioselectivity.Linear alkyls,branced alkyls and alkyls containing various functional groups were accepted in β-position.