Synthesis Of Ferrocenyl Phosphinothiourea Organocatalysts And Their Application In Asymmetric MBH Reaction

The Morita-Baylis-Hillman reaction is an atom-economic carbon-carbonbond-forming reaction between the-position of the activated alkenes （alkynes） andcarbon electrophiles under the influence of chiral tertiary phosphine or tertiary amineproviding diverse classes of densely functionalized molecules which were valuableintermediates in organic synthesis. We can obtain single chiral product by using chiralcatalyst. However, the reaction has traditionally suffered from the low chemical yields,slow reaction rate, and poor enantioselectivity, which has significantly restricted its furtherapplications. Therefore to design and synthesis efficient chiral catalysts for asymmetricMBH reaction are the core of the research.In recent years, the chiral bifunctional organocatalyst contained Lewis alkali andBronsted acid is becoming a hot spot of the research. This dissertation focused on the design and synthesis of ten novel ferrocenyl chiral phosphinothiourea organocatalysts andtheir application in asymmetric MBH reaction.The main contents are as followed:1. The ten novel ferrocenyl chiral phosphinothiourea organocatalysts were designedand synthesized from Uig’s amine as the original material. Firstly, Uig’s amine was joineddifferent groups of chiral tertiary phosphine through activation by s-BuLi. The primaryamine compounds were obtained through the reactions of esterification andammonification. Finally, the primary amine compounds condensed with the correspondingisothiocyanate to afford the ferrocenyl chiral phosphinothiourea organocatalysts（I~X）.Furthermore, the single crystal of（RC, SFe）-1-［3,5-bis（trifluoromethyl）phenyl］-3-｛1-［2-（diphenylphosphino）ferrocenyl］ethyl｝thiourea（Ⅰ）was obtained and the X-rayanalysis further confirmed its structure.2. The ferrocenyl chiral phosphinothiourea was firstly applied as organocatalyst inthe asymmetric MBH reaction of MVK and aromatic aldehydes. We got the asymmetricMBH reaction product of MVK and p-nitrobenzaldehyde with73%yield and54%ee byusing Ⅰ as the catalyst of the reaction. We have tried to use the ferrocenyl chiralphosphinothiourea as organocatalyst to catalyze the asymmetric MBH reaction ofcyclohexenone and aromatic aldehydes. Unfortunately, no MBH reaction product wasobtained.3. The ferrocenyl chiral phosphinothiourea was firstly applied as organocatalyst inthe asymmetric MBH reaction of HFIPA and aromatic aldehydes. The catalystⅠdisplayedhighly efficient for this reaction. The reaction proceeded in25℃for48h in the solvent ofTHF by adding10mol%Ⅰand5mol%NaOH. We got the excellent result of85%yieldand up to98%ee.4. We firstly found that NaOH could catalyze the MBH reaction of HFIPA andp-nitrobenzaldehyde. Furthermore, we also firstly found that the chemical yield and theenantioselectivity could be increased obviously by adding moderate inorganic alkali.