The Synthesis Of Optically Active 2,2'-Bis(Diphenylphosphino)-1,1'-binaphthyl(BINAP)

Asymmetric catalysis is having a revolutionary impact on the chemical syntheses of chiral compounds. The chiral catalysis 1,1'-Binaphthol and its derivatives BINAP complexes is the most succeeded case. By applying this asymmetric reaction, an important industrial process was realized. It is difficult to synthesis the optically active BINOL and BINAP and the price is expensive. For this reason, the research of this technology have remained limited in our country.Owing to the vast foreground of the optically active BINAP, we proposed a novel synthetic approach to this key intermediate.This thesis is study the synthesis of BINOL and its optical resolution according to previous research work. The oxidative coupling of 2-naphthols suspended in aqueous solution containing Fe³⁺, The results under traditional condition and microwave radiation are compared, the method of microwave radiation can be obviously shorten the reaction time, decrease about 11/12,the output efficiency can improved nearly 10%. Synthetic of resolving reagent using Ethanol as solvent under microwave radiation is the first, neither need the continuous and temperature controllable microwave reactor nor need react 3-4 hours. So there are have perfect applied volue under existing condition. The optical resolution of BINOL has been made with (8S,9R)-(-)-N-benzylcinchoninium chloride under Butyl Acetate.Synthesis of the optically active 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl(BINAP) is on the basis of earlier synthetic routes of BINAP, the starting raw material was changed and the crucial steps were improved. Using 1,1'-binaphthol as starting material, effect ester condensation with TrifluoromethaneSulfonic Acid, the output efficiency nearly 90%. NiCl₂·6H₂O react with triphenylphosphine in the Acetic acid solution under room temperature get NiCl₂·(PPh₃)₂ . the Diphenylphosphino's output efficiency nearly 70%.Finally, using NiCl₂(PPh₃)₂,DABCO and DMF as catalyzer process coupling reaction gained (S)-(-)-BINAP under the system without any water and oxygen. Instead of using NiCl₂·(dppe) as catalyst, the coupling reaction was conducted by NiCl₂·(PPh₃)₂ which is more accessible and the reaction rans smoothly. But this method have numerous setps, needs iterative wash, extraction, lead the efficiency is very lowly, only 37%. The infrared absortion spectra of samples is basically identical to the standard sample in the literature.