Synthesis And Application Of Chiral N-tert-butylsulfinyl Vinyl Aziridiens

Chirality is a common and mysterious phenomenon in nature. Almost all thebiological macromolecules are chiral, such as proteins, polysaccharides, nucleic acids.Meanwhile, chiral compounds play an important role on medicine, materials and otherfields. Therefore, to develop an efficient method to synthesize chiral compounds notonly shows an academic significance, but also a good prospect. Undoubtedly,asymmetric catalysis accords with the requirements for modern society, and is the bestapproach to prepare chiral compounds. Rhodium-catalyzed1,4-addition reaction hasoften been emphasized in the asymmetric synthesis. Currently, chiral ligands containingphosphorus, nitrogen, olefin, an oxygen and sulfur were broadly used forrhodium-catalyzed1,4-addition reaction as ligands. The chiral olefin-sulfoxide ligandshaven’t been applied until a few years ago, and have showed good potential in theasymmetric catalytic reactions.This thesis is to design and synthesize a new type of olefin-sulfoxide ligands andstudy the performance of these ligands for the rhodium-catalyzed asymmetric1,4-addition reaction of aryl boronic acids to α, β-unsaturated ketones. The idea is basedon the splendiferous stereo-control performance of tert-butyl sulfoxide and the novelcoordination ability of olefin, and a rigid three-membered ring with N-tert-butylsulfinylvinyl aziridines was introduced into the ligands. This is the first case that N-tert-butylvinyl aziridines with a rigid heterocyclic structure as chiral ligands have been used inasymmetric catalysis. By considering the effect of steric and electronic effects，wesynthesized nine chiral N-tert-butylsulfinyl vinyl aziridines ligands，which had differentgroups. With chiral N-tert-butylsulfinyl vinyl aziridines in hand, we chose the Rhcatalyzed1,4-addition of phenylboronic acid to cyclohexenone as the model reaction toevaluate their catalytic performance. The reaction was performed as followingconditions: temperature at70℃,[Rh(Cl)(C2H4)2]2as a catalyst,4mol/L KOH as abase,1,4-dioxane as solvent. The results shown that, stereochemistry of asymmetriccatalytic reaction is decided by chiral sulfur atom of N-tert-butylsulfinyl vinyl aziridinesligands, but not the chirality and relative configuration of rigid heterocyclic structures,which is an demonstrated rare phenomenon in the asymmetric catalysis reactions.The results indicated that the new type of chiral N-tert-butylsulfinyl vinylaziridines is very good ligands for the Rh catalyzed asymmetric1,4-addition. Theproduct could be obtained in99%of yield with99%ee. Having chose the optimalligand, we applied the optimal ligand in Rh-catalyzed1,4-addition with different typesof α, β-unsaturated ketone to different arylboronic acid. The result is excellent,affording the products in high yield(30%-99%) and high ee (30%-99%).