[2,3]-Sigmatropic Rearrangement Of Sulfonium Ylide Derived From Cu Carbene:Catalytic Asymmetric Trifluoromethylthiolation

[2,3]-sigmatropic rearrangement of sulfonium ylides derived from metal cabene are known Doyle-Kirmse reaction,provided an effective strategy to construct counpounds containing C-S bond.Using this method,we realized a highly enantioselective trifluoromethylthiolation reation between tert-butyl 2-diazo-2-(4-aryl)acetate and allyltrifluoromethyl sulfide catalyzed by chiral copper complex.The first part was mainly to synthesize substrates and chiral ligands.Phenylacetic acid was used as starting material to synthesize different substituted diazo coupounds through esterification and diazo transfer process.Allyltrifluoromethyl sulfide was synthesized by a one-pot reaction of allyl chloride,TMSCF3,sulphur,KF and CuSCN.A series of chiral bis(oxazoline)ligands with bi-substitution on the connected methylene were synthesized by two steps.The second part of the th esis was to explore the reaction system,By screening different substrates,ligands,solvents,temperature and other factors,the optimum reaction conditions were determined:we chose chiral copper-L5 complex as catalyst,p-xylene as solvent,then tert-butyl 2-diazo-2-(4-aryl)acetate reacted with allyltrifluoromethyl sulfide at 30? for 6 hours to produce final product in moderate to good yields and enantioselectivity.The highest yield is up to 98%,the highest enantioselectivity is up to 92%.This reation provides an effect access to synthesize organic compounds withn C-SCF3 bond.