The Reasearchs On The Reactions Of MBH Or MBH Esters And Analogues Catalyzed By Lewis Bases

Recently, chiral multifunctional phosphines have proven to be powerful synthetic tools in asymmetric organocatalysis, and have attracted much attention by chemists. This dissertation mainly focuses on two parts:i) Design and synthesis of a series of new chiral multifunctional phosphine catalysts based on a chiral binaphthyl scaffold for use in some asymmetric reactions; ii) Design and synthesis of a series of MBH carbonate analogues using Lewis bases as catalysts. Generally this paper can be divided into the following four parts:1Multifunctional chiral phosphines-catalyzed the allylic substitution of Morita-Baylis-Hillman (MBH) adducts:A series of new multifunctional phosphine-thioureas have been designed and synthesized and utilized in allylic substistution of MBH adducts with oxazolones. Good to excellent yields and ee’s as well as moderate to good de"s have been achieved by tuning nucleophilicity and steric hinderance of the reactive phosphorus center’s and the acidity of hydrogen-bonding. Finally, the optical multisubstituted amino-acid derivatives have been obtained by hydrolyzation.2New multifunctional chiral phosphines-catalyzed aza-Morita-Baylis-Hillman reaction:a series of new multifunctional and multiaxially chiral phosphine-amides derived from naphthidine have been designed and synthesized for use in aza-MBH reactions of5,5-disubstituted cyclopent-2-enones and N-Sulfonated Imines affording the corresponding optically active adducts in good to outstanding yields with moderate to good ee’s by means of combining chiral phosphine with binol.3Nitrogen containing Lewis bases catalyzed reactions of allenyl acetates with isatin derived oximes:New MBH analogues have been synthesized with high reactivity due to its two highly active moieties. Allenyl acetates were reacted with isatin-derived oximes catalyzed by different nitrogen containing Lewis bases, affording the corresponding oxime ethers or nitrones in good to high yields with high regio-and stereoselectivities. The mechanistic insights have been disclosed by control experiments and DFT calculations.4Lewis bases catalyzed reactions of new cyclopropenones with nucleophiles:new cyclopropenones have been synthesized for reacting with nucleophiles catalyzed by different Lewis bases produing the corresponding allenic esters in good to excellent yields.