The Syntheses Of Polyolefins With Pendant Of Binaphthyl And The Primary Application In Asymmetric Catalysis

Polymers with pendant of Binaphthyl were widely used in chiral recognition and unsymmetric catalysis. Scientists have designed and synthesised of many polymers with pendant of binaphthyl which modified by different groups, and many good results have been achieved. At present, there is few report about vinly monomer and vinly polymers with pendant of binaphthyl. In present work, the polyolefins with pendant of binaphthyl are synthesized and used in unsymmetric catalysis. The main research contents are as follow:(1)(S)-6-(2-chloroacetyl)-2,2′-dimethoxy-1,1′-binaphthyl was synthesized via Friedel-Crafts acylation of(S)-2,2′-dimethoxy-1,1′-binaphthyl and chloroacetyl chloride. In the presence of lithium aluminium hydride and anhydrous aluminium choride, the carbonyl group was reduction from(S)-6-(2-Chloroacetyl)-2,2′-dimethoxy-1,1′-binaphthyl to create(S)-6-(2-chloroethyl)-2,2′-dimethoxy-1,1′-binaphthyl.(S)-6-(2-chloroethyl)-2,2′-dimethoxy-1,1′-binaphthyl reacted with potassium hydroxide to create(S)-6-vinyl- 2,2′-dimethoxy-1,1′-binaphthyl.(2)(S)-2,2′-dihydroxy-1,1′-binaphthyl reacted with pivaloyl chioride to create(S)-2-hydroxy-2′-pivaloyloxy-1,1′-binaphthyl.(S)-2-hydroxy-2′-pivaloyloxy-1,1′-binaphthy reacted with Br2 to prepare(S)-6-bromo-2-hydroxy-2′-pivaloyloxy-1,1′-binaphthyl.(S)-6-bromo-2-hydroxy-2′-pivaloyloxy-1,1′-binaphthyl reacted with potassium hydroxide to give(S)-6-bromo-2,2′-dihydroxy-1,1′-binaphthyl.(S)-6-bromo-2,2′-dihydroxy-1,1′-binaphthyl reacted with Methoxymethyl chloride to create(S)-6-bromo-2,2′-bis(methoxymethoxy)-1,1′-binaphthyl.(S)-6-bromo-2,2′-bis-(methoxymethoxy)-1,1′-binaphthyl reacted with n-Bu Li and DMF to prepare(S)-6-formyl-2,2′-bis(methoxymethoxy)-1,1′-binaphthyl.(S)-6-vinyl-2,2′- bis(methoxymethoxy)-1,1′-binaphthyl were synthesized via Wittig reaction of(S)-6-formyl-2,2′-bis(methoxymethoxy)-1,1′-binaphthyl. The monomer(S)-6-vinyl-2,2′-bis(methoxymethoxy)-1,1′-binaphthyl was radically polymerized using AIBN as initiators. Poly-[(S)-6-vinyl-2,2′-bis(methoxy-methoxy)-1,1′-binap-hthyl] which was obtained by radical polymerizations was confirmed to exist in the form of one-handed helical structure by means of comparing the specific optical rotation and the CD spectra with that of monomer and model compounds such as(S)-6-ethyl-2,2′-bis(methoxy-methoxy)- 1,1′-binaphthyl.(3)(S)-3-Vinyl-2,2′-bis(methoxymethoxy)-1,1′-binaphthyl were synthesized via Wittig reaction.(S)-3-Vinyl-2,2′-bis(methoxymethoxy)-1,1′-binaphthyl reacted with HCl to yield(S)-3-Vinyl-2,2′-dihydroxy-1,1′-binaphthyl. And then(S)-3-Vinyl-2,2′-dihydroxy-1,1′-binaphthyl reacted with POCl3 and H2 O to create(S)-3-Vinyl-1,1′-binaphthyl-2,2′-diylhydrogenphate. The monomer(S)-3-Vinyl-1,1′-binaphthyl-2,2′-diylalkylphosphate was radically polymerized using AIBN as initiators.(4) The phosphate polymer were application in asymmetric catalysis Henry reaction. All catalytic reactions show positive inductions. Better enantioselective product could be obtained in asymmetric catalysis Henry reaction when used EtOH as an additive. We studied the enantioselective of L1* in the asymmetric catalysis Henry reaction, including the optimizing conditions and the extending of the substrate. We also studies the recycling of L1*.(5)(S)-3-vinyl-2,2′-dihydroxy1,1′-binaphthyl was radically polymerrized to create helical polymer. The application of polymer(L2*) in enantioselective borane reduction of ketones were conducted and the ee of the products was up to 99%.