两类新型含硫手性大环配体的合成  

The Synthesis of Two Series Novel Sulfur containing Chiral Macrocyclic Ligands

作　　者：张小玲[1] 黎星术[1] 谢如刚[1] 

机构地区：[1]四川联合大学化学系

出　　处：《高等学校化学学报》1998年第8期1262-1266,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：以Ｌ－半胱氨酸为手性源，合成了两类新型含硫手性大环配体，并进行了结构表征．Ｌ－半胱氨酸与二溴化合物反应生成双氨基酸，转变为双氨基酸酯后与双酰氯在高度稀释和无水条件下进行关环反应，制得环上含硫的手性大环配体３ａ－３ｅ．Ｌ－半胱氨酸经苄基化和硼烷还原后与对应的双对甲苯磺酸酯偶联生成手性二胺４ｆ－４ｈ，最后与２，６－吡啶二甲酰氯关环。In this paper, we report that two series of novel optically active sulfur containing macrocyclic ligands have been synthesized by using L cysteine as the source of chirality. The synthetic method is in the following: in the presence of NaHCO 3, L cysteine reacts with dibromoalkane to form bridged bis amino acids under a very mild condition, then, are transformed to the bis esters and cyclized with bis acid chlorides to give the targets 3a 3e. The other series are macrocyclic ligands with sulfur containing pendant. Firstly, L cysteine reacts with PhCH 2Cl to give β benzylthio L alanine, and then it is reduced to 2 amino 3 benzylthio propanol by BH 3·THF. The amino alcohol reacts with bis toluene p sulphonate of diethylene glycol to give the diamine 4f. The synthesis of 4g 4h is just like that of 4f.The cyclization of 4f 4h with 2,6 pyridinedicarbonyl dichloride gives the macrocyclic ligands 5f 5h. The structures proposed for these novel macrocycles are consistent with the data obtained from their 1 H NMR, MS and IR spectra and elemental analysis.

关 键 词：L-半胱氨酸 含硫手性大环配体 合成 表征 

分 类 号：O626[理学—有机化学] O641.4[理学—化学]