LC-induced Modification Of Double-helix Compounds Based On Binaphthyl Template

The optically active compounds that were synthesized from 2,2'-disubstituted binaphthyl template have a broad application prospects in asymmetric catalysis, molecular recognition, molecular self-assembly and new optoelectronic functional materials. Chiral nematic liquid crystals (N*-LC) with one binaphthyl unit have been reported and used to induce synthesis of conductive polyacetylene materials with one single helical direction. We synthesized a number of intramolecular double-helix compounds from chiral binaphthyl template in our preceding research work. These compounds have potential applications to photoelectric functional materials because of their unique structure and pure optical activity. Therefore, selective modification of the double-helix structure was described, a series of LC-induced primitives were introduced, and the target compounds which contain double-helix structure were obtained. These target compounds may have special liquid crystal properties, and may be a breakthrough as potential new photoelectric functional compounds.The second chapter focuses on the synthetic method of double-helix parent compounds (R,P)-20 and (R,P)-21. (R)-2,2'-dihydroxy-1,1'-binaphthyl with highly stable chiral configuration was employed as structural template to introduce chiral source, m-phenylene who has a good spatial orientation was used as the bridge for connection, and the reaction condition was controlled to make it benefit to intramolecular cyclization as far as possible. Finally, we obtained double-helix parent compounds in a good yield. According to convenient and economical principles, we designed two different routes to synthesize (R,P)-20 and (R,P)-21 respectively.A number of LC (liquid crystal)-induced segments with simple structure were designed and easily synthesized in the third chapter. Purification for aryl boronic acid segment 28 is not easy, while the impurities which mostly come from Grignard reagent system are hydrocarbons should be taken into account. In the next step, the Suzuki coupling reaction will not be adversely affected by these inactive impurities. So the residue was directly used for next step. Azide was introduced in LC-induced segments 31 and 33, so that Sharpless reaction for next step could proceed smoothly.The fourth chapter of this paper describes the synthesis of target compounds. Being included,16 was obtained directly by Suzuki coupling reaction for aryl boronic acid 28 and (R,P)-21. Firstly terminal alkynyl was introduced in (R,P)-20 through Sonagashira coupling reaction, while the intermediate 35 was synthesized. Then the target compound 17 was obtained by Sharpless reaction for 35 and the LC-induced segment 31,18 was obtained by Sharpless reaction for 35 and 33. Another double-helix derivative 19 which contains a new LC-induced primitive was synthesized from 18 and p-toluidine.Important intermediates and target compounds synthesized in this paper were characterized by IR,1H NMR,13C NMR and DEPT.