英格拉霉素右部片断的合成有机化学.pdfVIP

DOI: 10.6023/cjoc201307011 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 英格拉霉素右部片断的合成 高凯歌a 孙默然a 朱 明b 周 航a 曹其伟a 杨 华*,a (a 郑州大学药学院 郑州 450001) (b 海口市疾病预防控制中心 海口 571000) 摘要 英格拉霉素右部片断含有挑战性的手性叔醇结构. 以本实验室发展的[2,3]-Meisenheimer 重排为关键反应, 以D- 丝氨酸为起始原料, 经 Wittig 反应、[2,3]-Meisenheimer 重排、NaBH4 选择性还原酯基等 15 步反应, 合成了英格拉霉素 右部片断, 总收率为 28%, ee 值为 90%. 关键词 英格拉霉素; 手性叔醇; [2,3]-Meisenheimer 重排; Wittig 反应; NaBH4 选择性酯还原 Synthesis of Right Segment of Ingramycin Gao, Kaigea Sun, Morana Zhu, Mingb Zhou, Hanga Cao, Qiweia Yang, Hua*,a a ( School of Pharmaceutical Science, Zhengzhou University, Zhengzhou 450001) b ( Haikou Center for Diease Control and Prevention, Haikou 571000) Abstract The right segment of ingramycin contains a synthesis-challenging chiral tertiary alcohol structural motif. Based on methodology developed on our laboratory to construct chiral tertiary alcohols via [2,3]-Meisenheimer rearrangement, the syn- thesis of right segment of ingramycin was successfully achieved over fifteen steps via successive Wittig reaction, [2,3]-Meisenheimer rearrangement, selective ester group reduction with NaBH , and etc. The total yield was 28% and ee value 4 was 90%. Keywords ingramycin; chiral tertiary alcohol; [2,3]-Meisenheimer rearrangeme