SYNTHESIS OF (+/-)-FERRUGININE AND (+/-)-ANHYDROECGONINE METHYL-ESTER BY A TANDEM CYCLOPROPANATION COPE REARRANGEMENT
SYNTHESIS OF (+/-)-FERRUGININE AND (+/-)-ANHYDROECGONINE METHYL-ESTER BY A TANDEM CYCLOPROPANATION COPE REARRANGEMENT
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DOI：
10.1021/jo00019a044
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发表时间：
1991-09-13
影响因子：
3.6
通讯作者：
YOUNG, WB
中科院分区：
文献类型：
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作者：
DAVIES, HML;SAIKALI, E;YOUNG, WB
在N-（烷氧羰基）吡咯的存在下，醋酸铑（II）催化乙烯基重氮甲烷的分解，合成了8-氮杂双环[3.2.1]辛-2，6-二烯。 由具有单个吸电子基团的乙烯基重氮甲烷产生的乙烯基类卡宾在乙烯基末端除了类卡宾位点之外还表现出竞争反应性。 然而，通过适当选择催化剂和溶剂，良好的区域控制是可能的。 通过（+/-）-ferruginine、（+/-）-anhydroecgonine甲酯和（+/-）-anatoxin a的低级同系物的短时间合成，证明了这种新方法对托烷生物碱的实用性。
Rhodium(II) acetate catalyzed decomposition of vinyldiazomethanes in the presence of N-(alkoxycarbonyl)pyrroles led to the synthesis of 8-azabicyclo[3.2.1]octa-2,6-dienes. The vinylcarbenoids generated from vinyldiazomethanes with a single electron-withdrawing group exhibited competing reactivity at the vinyl terminus in addition to the carbenoid site. Good regiocontrol was possible, however, by appropriate choice of catalyst and solvent. The practicality of this new approach to tropane alkaloids was demonstrated through short syntheses of (+/-)-ferruginine, (+/-)-anhydroecgonine methyl ester, and the lower homologue of (+/-)-anatoxin a.