以廉价易得的苯酚和马来酸酐为原料, 经直接酰基化、I2催化下分子内关环、环丙烷化、酯化、然后成肟得(1aRS,7aRS)-7-羟基氨亚基-1,1a,7,7a-4H-丙环骈[b]色烯-1a-甲酸乙酯及其衍生物的有效全合成及其系列的衍生物. 本研究改进了色酮骨架的构建方法, 并采用约翰逊–科里–柴可夫斯基反应进行色酮骨架上的环丙烷化反应. 所有中间体以及目标产物的结构均由1H NMR, 13C NMR和ESI-MS确证. 该路线5步反应的总收率为20.1%~29.5%.
Abstract：
Ethyl 7-(hydroxyimino)cyclopropa[b]chromen-1a-carboxylate and their derivatives have been synthesized through directed acylation, intramolecular cyclization under the catalysis of iodine, cyclopropanation, esterification and oximation by using phenol and maleic anhydride as starting materials. In the current invetigation, the construction of chromone scaffold was improved and the cyclopropanation upon the treatment of Corey's dimethyloxosulfonium methylide was applied. The structures of all the intermediates and final products were confirmed by 1H NMR, 13C NMR, and MS, respectively. The overall yields of these 5-step procedures were 20.1%~29.5%.
许男徽, 陈河如. (1aRS,7aRS)-7-羟基氨亚基-1,1a,7,7a-4H-丙环骈[b]色烯-1a-甲酸乙酯及其衍生物的有效全合成[J]. 有机化学, 2015, 35(5): 1033-1039
