手性双苯并噁嗪-2-酮二酚衍生物的高效合成及其在不对称催化中的应用  

Efficient and Stereoselective Synthesis of the Chiral Dihydroxy-bisquinazoline-dione Derivatives and Their Application in Asymmetric Catalysis

作　　者：林伟[1] 蔡琦[1] 郑纯智[1] 黄志斌[2] 史达清[2] 

机构地区：[1]江苏理工学院化学与环境工程学院,常州213001 [2]苏州大学材料与化学化工学部,苏州215123

出　　处：《有机化学》2017年第8期2094-2100,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21502074);江苏省高校自然科学重大研究(No.15KJA150006)资助项目~~

摘　　要：探索了手性苯并噁嗪-2-酮二酚衍生物的高效合成,以甲氧基取代的2-羟基苯甲醛衍生物和手性环己二胺为起始原料合成手性双亚胺,后经低价钛促进下还原、偶联与固体光气作用,构建了含有甲氧基的手性苯并噁嗪-2-酮衍生物,通过官能团转化,利用三溴化硼还原得到相应的手性苯并噁嗪-2-酮二酚衍生物.在此基础上,考察了手性苯并噁嗪-2-酮二酚催化剂在醛与二乙基锌不对称加成中的应用.此方法为合成手性苯并噁嗪-2-酮二酚衍生物提供了一条有效途径.An efficient and simple method for the synthesis of chiral benzo[5,6][1,3]oxazino[4,3-c]quinoxaline-dione is reported. 2-Hydroxybenzaldehydes and diamines were utilized as the starting materials, the formed diimines then underwent a reductive-cyclization process with triphosgene to give bis-quinazoline-dione derivatives induced by low-valent titanium reagent. Then through the conversion of functional groups, the bis-quinazoline-dione compounds containing hydroxy group have been obtained from their corresponding compounds containing methoxy group in the presence of BBr3. In addition, the dihydroxy-bis-quinazoline-dione derivatives were applied on the asymmetric nucleophilic addition of Et2 Zn to aldehydes.The reported method is the efficient approach for the synthesis of dihydroxy-bis-quinazoline-dione derivatives.

关 键 词：双苯并噁嗪-2-酮 不对称 合成 

分 类 号：O621.251[理学—有机化学] O626[理学—化学]