由α-氨基亚甲基膦酸酯构建偕二胺衍生物  

An Access to the gem-Diamine Derivatives from α-Carbamatemethylphosphonate

作　　者：黄晓丽[1] 任林静[1] 蒲家志[1] 贺春阳 姚秋丽[1] Huang Xiaoli Ren Linjing Pu Jiazhi He Chunyang Yao Qiuli(School of Pharmacy, Zunyi Medical University, Zunyi, 56300)

机构地区：[1]遵义医学院药学院,遵义563000

出　　处：《有机化学》2017年第9期2369-2376,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金基金(No.21462056);贵州省联合基金(No.[2014]7542);贵州省大学生创新(No.201610661006)资助项目~~

摘　　要：报道了由α-氨基亚甲基膦酸酯构建膦酸酯的偕二胺衍生物的研究.在前期的研究中,磺砜与磷酸二乙酯的反应主要生成产物α-氨基亚甲基膦酸酯;当降低磷酸二乙酯的用量时,检测到另一副产物——α-氨基亚甲基膦酸酯的偕二胺衍生物.研究表明这一类独特的化学结构具有潜在的抗癌活性,但关于其合成的研究报道很少,针对这一背景,进一步研究了这一类型化合物的合成方法学.以石油醚作为溶剂,在氢氧化锂碱性条件下,α-磺酰烷氨基甲酸酯与α-烷氧酰胺亚甲基膦酸酯反应,能以良好至优秀的产率顺利地合成α-氨基亚甲基膦酸酯的偕二胺衍生物.该方法操作简便,条件温和,底物适用性广.The preparation of gem-diamine derivatives of phosphonates from α-carbamatemethylphosphonates is reported. In our earlier work, the reaction of sulfone with dialkylphosphonate gave α-carbamatemethylphosphonate as the major product. However, gem-diamine derivative of phosphonate was unexpectedly formed as a side product when decreasing the amount of dialkylphosphonate. Although few reports exist on the synthesis of this unique structure, gem-diamine derivatives have shown potential biological activity as an anti-cancer reagent. After optimization, a methodology for the synthesis of gem-diamine derivatives of α-carbamatemethylphosphonate is provided. The reaction of α-carbamatemethylsulfone with α-carbamatemethylphosphonate using Li OH as a base and commercial petroleum ether as solvent provided gem-diamine derivatives in good to excellent yields. This simple protocol runs under very mild conditions, and has a broad substrate scope.

关 键 词：α-氨基亚甲基膦酸酯 偕二胺衍生物 磺砜 

分 类 号：O621.3[理学—有机化学] TQ460.1[理学—化学]