Syntheses And Preliminary Application In Asymmetric Catalysis Of Binaphthylene Derived Olefin Polymers

DNA with a helical structure has received widespread attention due to its special properties.This has led researchers to have great interest in the synthesis and application of polymers with helical structures.Optically active 1,1’-binaphthol（BINOL）derivative with a special skeleton,contains a number of modifiable sites and its hydroxyl groups can be coordinated with organometallic or inorganic nitrogen,oxygen,phosphorus,etc.are therefore widely used in organic asymmetric synthesis,chiral recognition,fluorescence recognition,etc.So,how to combine the advantages of BINOL derivative with the potential application of spiral polymers will be a very significant issue.（1）With bis（tri-phenylphosphine） nickel（II） chloride（NiCl₂（Ph₃P）₂） as the catalyst,（S）-3-iodo-2,2’-bis（methoxymethyl）-1,1’-binaphthyl reacted with 2,4,6-triisopropyl-phenylmagnesium bromide gived（S）-3-（2,4,6-triisopropyl） phenyl-2,2’-bis（methoxyme-thyl）-1,1’-binaphthyl.（S）-3-（2,4,6-Triisopropyl） phenyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl reacted with ⁿBuLi and N,N’-dimethyl formamide（DMF） to afforded（S）-3-（2,4,6-triisopropyl） phenyl-3’-formyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl.Then chiral monomer（S）-3-（2,4,6-triisopropyl） phenyl-3’-vinyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl was obtanied via witting reaction of （S）-3-（2,4,6-triisopropyl）phenyl-3’-formyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl.Poly-（S）-3-（2,4,6-triisopropyl） phe-nyl-3’-vinyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl（poly-BNO-1） was given by radical polymerization with AlBN as the initiator.By comparing the specific rotation,UV-vis absorption spectra,and circular dichroism spectra（CD）of poly-BNO-1 and its corresponding monomer and monomer unit analogs,it was confirmed that poly-BNO-1 with a one-chiral helical conformation.（2）Poly-（S）-3-（2,4,6-triisopropyl）phenyl-3’-vinyl-1,1’-binaphthyl-2,2′-diylhy-drogenphate（poly-BNPO-3a and poly-BNPO-3） was obtained in two ways.1).（S）-3-（2,4,6-triisopropyl）phenyl-3’-vinyl-1,1’-bi-2-naphthol was obtained by deprotection of the MOM groups in hydrochloric acid of the chiral monomer（S）-3-（2,4,6-triisopropyl）phenyl-3’-vinyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl.Then（S）-3-（2,4,6-triisopropyl） phenyl-3’-vinyl-1,1’-bi-2-naphtholreacted with phosphorus oxychloride and water to gived chiral monomer（S）-3-（2,4,6-triisopropyl） phenyl-3’-vinyl-1,1’-binaphthyl-2,2′-diylhydrogenphate.By radical polymerization with AlBN as the initiator,Poly-（S）-3-（2,4,6-triisopropyl） phenyl-3’-vinyl-1,1’-binaphthyl-2,2′-di-ylhydrogenphate（poly-BNPO-3a） was given.2).Poly-（S）-3-（2,4,6-triisopropyl） phenyl-3’-vinyl-1,1’-bi-2-naphthol（poly-BNO-2） was obtained by deproted the MOM groups in hydrochloric acid of the chiral poly-（S）-3-（2,4,6-triisopropyl）phenyl-3’-vinyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl（poly-BNO-1）.Then poly-BNO-2 reacted with phosphorus oxychloride and water yielded poly-（S）-3-（2,4,6-triisopropyl） phenyl-3’-vinyl-1,1’-binaphthyl-2,2′-diylhydrogenphate（poly-BNPO-3）.Comparing the nuclear magnetic proton spectrum（¹H NMR）,molecular weight（Mn）,polymer dispersibility（PDI）,and specific optical rotation of the polymers poly-BNPO-3a and poly-BNPO-3 obtained in two different ways,the polymerization parameter of poly-BNPO-3 was significantly superior to that of poly-BNPO-3a.（3）The monomer（S）-3-（4-vinylbenzyloxy） methyl-2,2’-bis（methoxymethyl）-1,1’-binaphthyl was synthesized.With radical polymerization and deprotection of the MOM groups,we get poly[（S）-3-（4-vinylbenzyloxy） methyl-1,1’-binaphthyl]（poly-5）.The poly-5 was applied to the heterogeneous asymmetric catalytic reaction of chalcone,The reaction yielded high yield and obtained in good enantioselectivity with up to 99%ee.Then the poly-5 was applied to the homogeneous asymmetric addition of triethylaluminum to aromatic aldehyde,and the reaction obtained extremely high yield with up to 98%,and the enantioselectivity were good too,up to 99%ee.By studying the asymmetric induction effect of polymer poly-5 in these two reactions,we can know that poly-5 has excellent induction effect in homogeneous asymmetric reaction and heterogeneous asymmetric reaction.