The Design And Synthesis Of Enantiopure Cyclophynes With 2, 2'-Binaphthyl Template

The synthesis of cyclophynes and their applications in various fields are reviewed in this paper based on a large number of references. After several decades'development, the chemistry of cyclophynes has become a major component of supramolecular chemistry, of molecular recognition, of the building blocks for organic catalysts, receptor models, crown ethers, cryptands and of carbon-rich chemistry. The previous work of our lab was described, and a series of new type of cyclophynes and their derivatives were designed and synthesized.Because of the stability of binaphthalene's configuration in the reactions and the fine directional function of ethynyl in the space, enantiopure 2,2'-diethynyl-1,1'-binaphthyl was used as synthetic template for the synthesis of target molecules. In the second chapter in this paper, the synthesis of enantiopure [(R)- or (S)-form] 2,2'-diethynyl-1,1'-binaphthyl was described. Enantiopure (R)- or (S)-binapythol can be purchased conveniently and was a good material. 2,2'-Diethynyl-1,1'-binaphthyl was synthesized from binapythol by esterification of hydroxyl, Kumada reaction of sulfonic ester with Grignard reagent, bromination of methyl, hydrolyzation of dibromomethyl and especial Wittig reaction.In the third chapter, the design and synthesis of enantiopure compounds with cage structure were described. Enantiopure molecule square--(R,R,R,R)- and (S,S,S,S)-95 were synthesized from (R)- and (S)-2,2'-diethynyl-1,1'-binaphthyl templates by four steps including the introduction of protecting group, intermolecular coupling reaction, removal of protecting group, and intermolecular cross-coupling cyclization. In order to enhance the cavity sizes of compounds, a series of compounds with different length linkages of p-phenylene groups between 2,2'-diethynyl-1,1'-binaphthyl, including (R,R,R,R)-96, (R,R,R,R)-97 and (R,R,R,R)-98, were also designed and synthesized in this paper. In addition, via the linking of m-phenylene, compounds (R,R,R,R)- and (S,S,S,S)-99, (R,R,R,R,R,R)-100, (R,R,R,R,R,R,R,R)- and (S,S,S,S,S,S,S,S)-101 with cage structure were designed and synthesized from (R)- and (S)-2,2'-diethynyl-1,1'-binaphthyl templates. These compounds have the same building block and involve four, six and eight units of binaphthyl, respectively. In the synthesis of compounds (R,R,R,R)-95 and (S,S,S,S)-95, the decomposition of TMS group in common Eglinton reaction was successfully avoided by the homocoupling of alkyne under Sonogashira reaction condition. The circular dichroism (CD) spectra, specific rotations ([α]D25) and UV spectra of these compounds were characterized. Their CD spectra represented exactly mirror images of each other, which reflected unambiguously enantiomeric relation between two isomers. The space models of these compounds were obtained and the cavity sizes of these compounds were calculated using Chem3D. The cavity sizes of the target compounds were 1.0-2.3 nm, which are 1-3 times of the diameter of C60. Study on the cavity sizes of these compounds is of great significance to host-guest chemistry.In the fourth chapter, compounds (R,P)-102 and (R,P)-103 with double helical structure were designed and synthesized from (R)-2,2'-diethynyl-1,1'-binaphthyl by the introduction of protecting group, the connecting of linking bridges and intramolecular Sonogashira reaction. In the last intramolecular Sonogashira reaction, a syringe pump that can control the dropping rate of reactant solution was used in order to avoid the high concentration of reactant. The high concentration of reactant will produce intermolecular Sonogashira and Eglinton reaction. By using the syringe pump, the yields of the last step of intramolecular Sonogashira reaction were greatly improved.In the fifth chapter, several enantiopure Dumbbell-compounds [(R,P),(R,P)]-104-106 and dentritic compound [(R,P),(R,P),(R,P)]-107 with helical units were synthesized from (R)-2,2'-diethynyl-1,1'-binaphthyl by Sonogashira coupling reaction. In the structures of these compounds, cyclophyne bearing helical structure and rigid phenylethynyl were used as the ball of dumbbell and linking bridge, respectively. The synthesis of these compounds is a big challenge because abount 15 steps are required for each compound. Compounds 104-107 were successfully synthesized after great efforts, and their space models were given using Chem3D. The molecular sizes of compounds 104-107 are 2-3 nm, which makes these compounds have potential application as nanomaterials.All the intermediates and target compounds synthesized in this paper were characterized by MS, IR, 1H NMR, 13C NMR and DEPT.