由α-氨基亚甲基膦酸酯构建偕二胺衍生物
收稿日期: 2017-02-15
修回日期: 2017-05-04
网络出版日期: 2017-05-04
基金资助
国家自然科学基金基金（No.21462056）、贵州省联合基金（No.[2014]7542）及贵州省大学生创新（No.201610661006）资助项目
An Access to the gem-Diamine Derivatives from α-Carbamatemethylphosphonate
Received date: 2017-02-15
Revised date: 2017-05-04
Online published: 2017-05-04
Supported by
Project supported by the National Natural Science Foundation of China (No. 21462056), the Science and Technology Foundation of Guizhou Province (No.[2014]7542) and the Education Department of Guizhou Province (No. 201610661006).
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.
关键词： α-氨基亚甲基膦酸酯; 偕二胺衍生物; 磺砜
黄晓丽 , 任林静 , 蒲家志 , 贺春阳 , 姚秋丽 . 由α-氨基亚甲基膦酸酯构建偕二胺衍生物[J]. 有机化学, 2017 , 37(9) : 2369 -2376 . DOI: 10.6023/cjoc201702016
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 LiOH 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.
Key words： α-carbamatemethylphosphonate; gem-diamine derivatives; sulfone
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