Synthesis Of Ferrocenyl Multifunctional Organophosphorus Catalyst And Their Application In Asymmetric MBH Reaction

Asymmetric organic catalysis is one of the most active research fields in organic chemistry, as the classic of asymmetric reactions, Morita-Baylis-Hillman reaction has draw more and more attention of chemists scince the 1980 s. Recent research also suggests that the reaction possess extensive application prospect and developmental potential in organic synthesis. The MBH reaction, which mainly makes aldehyde together with polyene to generate more functional groups, has the basic characteristics same with efficient synthetic methods, such as atom economy, moderate reaction condition, reaction enantioselectivity, and the products have multiple functional groups that can be further converted. However, slow reaction speed, low yield and poor selectivity have always been the limitation of the application of asymmetric MBH reaction.Therefore,design and synthesis of more efficient chiral organic catalysts is always the important research content in the asymmetric MBH reaction.The previous studies of our team achieves exciting results. The thesis further designed and synthesized dual functional and multi-functional micromoleculed organic catalysts that based on the ferrocene skeleton on the basis of preliminary experiment, and lucubrate the catalytic activity in asymmetric MBH reaction.The maincontents are divided into the following several aspects:1.(R)-Ugi's amine, as the original material, activated by tertiary butyl lithium to introduce the tertiary phosphine group. It needs further two steps of esterification and aminolysis to get the intermediates of phosphonic chiral amine intermediates.Then isothiocyanates respectively condenses with different chiral primary amine intermediates, obtaining four kind of new-type chiral bifunctional catalysts ?~?. The starting material 1,1'-Bi-2-naphthol, activated by n-butyl lithium, introduced aldehyde group at the third-carbon position, and condensed with primary amine intermidiates to generate four kinds of multifunctional organocatalyst ? ~?.2. The ferrocenyl chiral organocatalyst was applied in the asymmetric MBH reaction of MVK and aromatic aldehydes. By optimizing the proportion of catalyst, such as solvent, temperature, substrate, etc, catalyst ? gives 93% of chemical yield, but not ideal for enantioselectivity,which is only 9% ee. We also have attempt to catalyze the asymmetric MBH reaction of acrolein and aromatic aldehydes, though achieves 91% yield, the enantioselectivity is only 4% ee.3. The multifunctional catalysts were also applied in asymmetric intermolecular MBH reaction, surprisingly to found that they had excellent chemical yield. The catalyst ? obtained 91% chemical yield in the same condition, which reacts only 12 h, while selectivity is less satisfactory, only achieved 15% ee.4. To further study the potential of the chiral catalysts, they were tested in the asymmetric MBH reaction of 1,1,1,3,3,3-Hexafluoroisopropyl acrylate with 4-nitrobenzaldehyde.We were excited to find that it only need 5 minutes for catalyst ? to end the reaction at room temperature, through optimizing conditions to obtain up to 99.7% ee.