Design Of Synthetic Organic Catalyst Proline, Cinchona Alkaloid And Its Derivatives And In Various Asymmetric Reactions

Asymmetric organic synthesis is one of the most active areas in thedevelopment of modern organic synthesis. Asymmetric synthesis is characteredwith high stereoselectivity, economy and ease of industrialization and so on,which play an important role in drug synthesis and efficacy analysis. To find anefficient and highly stereoselective catalysts system in a variety of asymmetriccatalytic reactions has become one of the goals that people pursue. In thispaper we design and synthesize a series of cinchona alkaloids andproline-based skeleton structure of novel chiral catalysts and apply them to avariety of asymmetric catalytic reactions.MethodsA variety of proline derivatives were designed and synthesized, catalyst,adjacent to, and on two benzene amine as raw material and L-proline viaamidation reaction, proline derivative catalysts for the synthesis of3kinds of C2symmetric structures. For the asymmetric Aldol reaction of substitutedbenzaldehyde and acetone and cyclohexanone, and the effect of temperature,catalyst and its quantity, auxiliary catalyst and solvent on the reaction selectivityeffects. Asymmetric synthesis of aza-Michael7cinchona alkaloid derivatives asthe catalyst of organic catalysts used in chalcone and aniline and its derivativesin addition reaction, the effects of solvent, temperature and Lewis acid and otherfactors on the reaction selectivity of7kinds of cinchona alkaloid derivatives asorganic catalyst for β-naphthol and N-Ts aromatic imide asymmetryaza-Friedel-Crafts was prepared by the reaction of Betti base derivatives. Theinfluence of solvent, temperature and amount of catalyst on catalytic performance.ResultScreening of different catalysts and in different reaction in the application ofoptimal catalyst system is as follows: the proline1A solvent wasdichloromethane; the amount of catalyst to substrate10mol%auxiliary catalyst,acetic acid is300mol%, the temperature of0oC. Get the anti configuration ofmain product in the reaction conditions, the yield of82%-92%, enantioselectivityup to90%ee, non enantioselectivity up to anti/syn=83/17EE, cinchona alkaloidscreening out the best catalyst for catalytic system:1D,10mmol%TBSCl+KI,no solvent, room temperature reaction. The asymmetric aza-Michael and itsapplications in9different chalcone and aniline addition reaction got up to thestereoselectivity of81%ee Friedel Crafts the best catalytic conditions for the10mmol%catalyst, toluene as solvent,0oC reaction. The chemical yield of70-86%and up to80%ee enantioselectivity.ConclusionThrough the synthesis of proline, cinchona alkaloid derivatives, and itsapplication to Aldol, mechea, Friedel Crafts reaction, showed different catalyticactivity, by adjusting the amount of catalyst, reaction temperature, solvent andauxiliary catalyst can increase the catalytic activity, establish the optimalcatalytic system, in this system development of different catalyst adaptation thesubstrate width.