Preparation And Application Of Microgel-Supported Chiral Ts-DPEN And Its Derivant In The Asymmetric Synthesis

As one of the most important methods to synthesis chiral compounds, because of its high performance in catalysis reaction, low usage, mild reaction conditions and reusability, asymmetric catalysis reactions become the most important way of chiral synthesis. Chiral sulfonyl diamine(Ts-DPEN) is an efficiency chiral catalyst which has been widely studied for decades. Use chiral Ts-DPEN and its derivatives to catalyze the asymmetric transfer hydrogenation, asymmetric Aldol condensation, asymmetric Micheal addition have achieved a very good results. Because of the chiral catalyst’s high price and complicated process to recycle which limits its application in the actual production.In order to solve the problem of catalyst’s reuse, supported catalyst is one of the most hopeful solutions. The traditional support was unsolvable inorganic materials, resin and soluble organic polymers. Among them the soluble organic polymers have been wild used because it can take part in hemogenous reaction, so it got a very high speed of reaction and could be detect by on-line measuring. Microgels is a kind of intramolecular cross-link polymers, due to its high specific surface area, low dispersed solution viscosity, stability of dispersion and good solubility in low temperature conditions make the microgels became a kind of high performance supporter in organic synthesis.In this paper, we use the microgels as a soluble supporter and two chiral Ts-DPEN derivants was synthesized, and this two kinds of microgels support chiral Ts-DPEN and its derivants was used to catalyze the asymmetric transfer hydrogenation and asymmetric Aldol condensation.In the chapter one, we reviewed chiral diamine and its derivatives of small molecules and different carrier supported chiral diamine kind of catalyst in the application of asymmetric catalytic reaction, and based on this, puts forward the paper’s ideas for design.In the chapter two, by five steps, include benzoin condensation, oxygenization, cyclization reactions, chiral separation, using benzaldehyde as the initiating material to synthise chiral DPEN. After that, chiral DPEN was react with4-vinylbenzene-sulfonyl chloride and then copolymerized with different crosslinker and get four kinds of microgels with different internal structures and characterize it. We use the micrgels support chiarl Ts-DPEN complex with [RuCl2(cycmene)]2and catalyze the asymmetric transfer hydrogenation. Discuss the affect of different solvent, temperature, S/C and internal structure to microgels support chiral Ts-DPEN’s catalytic effect and get the best reaction condition. Under the best reaction condition, we used the different substrate to study the different functional group of substrate’s effect to asymmetric transfer hydrogenation. These polymeric catalysts can be easily from the reaction mixture and recycled4times without a significant loss in catalytic activity.In the chapter three, we use the Ts-DPEN derivatives react with L-Boc-proline to get a chiral Ts-DPEN derivatives with proline structure, and copolymerized with styrene and divinylbenzene to synthetize microgels support chiral Ts-DPEN-Proline catalyst. and successfully applied to catalyize the asymmetric Aldol reaction between aromatic aldehyde and ketone. Discuss the affect of different solvent, temperature to the asymmetric Aldol reaction and get the best reaction condition. The polymeric catalysts can be easily separated through the recrystallization and filtering. The polymeric catalysts could be used for four time without a significant loss in catalytic activeity.In chapter four, we concludes the whole paper.