L-脯氨酸衍生的手性N,P-配体的合成及其在不对称1,3-偶极环加成反应中的应用有机化学.pdfVIP

DOI: 10.6023/cjoc201301080 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE L-脯氨酸衍生的手性N,P-配体的合成及其在 不对称1,3-偶极环加成反应中的应用 陈 虹 陈 谦* (哈尔滨工业大学基础与交叉科学研究院 城市水资源与水环境国家重点实验室 哈尔滨 150080) 摘要 从 L-脯氨酸衍生而来的酰胺膦类化合物 1, 经脱去保护基得到的氨基膦 2, 用正丁基锂处理后, 用 2- 甲氧基吡啶 类化合物捕获, 得到一类吡啶型的手性 N,P-配体 4; 氨基醇与碳酸二乙酯生成的噁唑啉酮 6, 与四氟硼酸三乙氧基鎓盐 反应制得的乙氧基噁唑啉 7 直接与氨基膦 2 反应, 合成了噁唑啉型手性 N,P-配体 8. 将两类手性 N,P-配体应用于 Ag(I) 催化的 1,3-偶极环加成反应, 通过对反应条件进行优化, 发现手性 N,P-配体与 AgOTf 所形成的催化剂能很好地催化 1,3-偶极环加成反应, 最高可以以 93%的收率获得环加成产物, ee 值最高可以达到 15%. 关键词 L-脯氨酸; 手性 N,P-配体; 1,3-偶极环加成 Synthesis of Chirl N,P-ligands Derived from L-Proline and Its Application to 1,3-Dipolar Cycloaddition Chen, Hong Chen, Qian* (State Key Laboratory of Urban Water Resource and Environment Academy of Fundamental and Interdisciplinary Science, Harbin Institute of Technology, Harbin 150080) Abstract Aminophosphine 2 was obtained by deprotection of amidophosphine 1, which was derived from L-proline. Depro- tonation of aminophosphine 2 with n-BuLi, and then being captured by 2-MeO-pyridine gave chiral pyridyl N,P-ligands 4. Reaction of aminoalcohol and diethyl carbonate afforded oxazolidione 6, which was converted to compounds 7 by the reaction with triethyloxonium tetrafluoroborate. Chiral N,P-ligands 8 were obtained by the reaction of compounds 7 with amino- phosphine 2. Two kinds of chiral N,P-ligands shown excellent catalytic activity in Ag(I) catalytic asymmetric 1,3-dipolar cycloaddition, and up to