Tertiary Amine-or Phosphine-catalyzed Annulations Of Activated Alkenes And Asymmetric Aza-Morita-Baylis-Hillman Reaction Of Ketimines

Recently, chiral phosphines are widely used in catalytic asymmetric organocatalysis, and become an active area in asymmetric organocatalysis. This dissertation mainly focuses on:(1) tertiary phosphine-catalyzed annulations of activated allenes, MBH carbonates and activated dienes, affording functionalized five-memberd or six-memberd compounds;(2) chiral phosphine or amine-catalyzed asymmetric aza-Morita-Baylis-Hillman (aza-MBH) reaction, giving the optically active3-amino-2-oxindoles bearing quaternary stereogenic centers. The dissertation is concretely divided into four parts:Part I:Tertiary phosphine and SPTS-catalyzed [4+2] annulations of activated allenes with ethyl2-(2-hydroxyaryl)-2-oxoacetates. A fairly efficient [4+2] annulation reaction of allenic ester or allenylsulfone with ethyl2-(2-hydroxyaryl)-2-oxoacetates catalyzed by tertiary phosphine and SPTS, respectively, has been developed, which provides an easy access to the synthesis of the corresponding quaternary carbon centered chroman derivatives under mild reaction conditions in moderate to good yields.Part II:Chiral phosphine-catalyzed asymmetric annulations of MBH carbonates.(1) Based on our previous work, a fairly efficient [3+2] annulation reaction of2-arylideneindane-1,3-diones with MBH carbonates catalyzed by bifunctional thiourea-phosphine catalysts has been disclosed, giving the functionalized cyclopentenes under mild reaction conditions in moderate to good yields (up to75%), with high diastereoselectivities (up to>99:1) and enantioselectivities (up to98%);(2) The asymmetric [4+1] annulations of a,(3-unsaturated ketones with MBH carbonates catalyzed by bifunctional thiourea-phosphine catalyst derived from an axially chiral binaphthyl scaffold has been developed, producing spirooxindoles containing two adjacent tertiary stereocenters with a good outcome.Part III:Chiral amine-or phosphine-catalyzed asymmetric aza-MBH reaction of ketimines derived from isatin with methyl vinyl ketone (MVK). The asymmetric aza-MBH reaction of isatin-derived N-Boc ketimines with MVK catalyzed by chiral amine and phosphine has been developed for the first time, which provides an highly efficient and enantioselective synthesis of3-amino-2-oxindoles bearing quaternary stereogenic center. Further mechanistic investigations elucidate that no non-linear effect was observed in this reaction.Part IV:Phosphine-catalyzed asymmetric formal [4+2] tandem cyclization of activated dienes with isatylidene malononitriles. The first highly enantioselective formal [4+2] tandem cyclization between isatylidene malononitriles and activated dienes catalyzed by bifunctional chiral phosphine catalysts has been disclosed, yielding the multi-stereogenic spirocyclic oxindoles in high yields along with excellent enantioselectivities and diastereoselectivities. This reaction is proposed to proceed via Rauhut-Currier/Michael/Rauhut-Currier reaction sequence. Sequences of transformations are also conducted for synthesis of polycyclic compound with the same enantiomeric excess.