Total Synthesis of (+)-Myriocin and (−)-Sphingofungin E from Aldohexoses Using Overman Rearrangement as the Key Reaction
Total Synthesis of (+)-Myriocin and (−)-Sphingofungin E from Aldohexoses Using Overman Rearrangement as the Key Reaction
复制标题
以 Overman 重排为关键反应，从己醛糖全合成 (+)-Myriocin 和 (−)-Sphingofungin E
DOI：
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发表时间：
2002
期刊：
影响因子：
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通讯作者：
N. Chida
中科院分区：
文献类型：
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作者：
T. Ōishi;K. Ando;K. Inomiya;Hideyuki Sato;M. Iida;N. Chida
描述了从醛己糖开始的天然α-取代α-氨基酸的全合成，(+)-肉豆肉素(1)和(−)-鞘真菌素E(2)。由d -甘露糖衍生的烯丙基三氯乙酸酯6E的Overman重排有效地生成了四取代碳与氮，随后的Wittig烯烃使肉豆蔻素的高官能化部分3具有立体选择性。砜介导的烯丙基溴3与C12疏水性组分4的偶联反应成功构建了含e-烯烃28的碳骨架。去除砜和保护基团完成了手性和立体选择性全合成(+)-肉豆蔻素(1)。从d -葡萄糖开始的类似转化也完成了(−)-sphingofungin E(2)的全合成。
Total synthesis starting from aldohexoses of naturally occurring α-substituted α-amino acids, (+)-myriocin (1) and (−)-sphingofungin E (2), is described. Overman rearrangement of allylic trichloroacetimidate 6E derived from D-mannose effectively generated the tetrasubstituted carbon with nitrogen, and subsequent Wittig olefination afforded the highly functionalized moiety 3 of myriocin stereoselectively. Sulfone-mediated coupling reaction of the allyl bromide 3 with C12 hydrophobic part 4 successfully constructed the carbon framework possessing E-olefin 28. Removal of the sulfone and protecting groups completed the chiral and stereoselective total synthesis of (+)-myriocin (1). A similar transformation starting from D-glucose also accomplished the total synthesis of (−)-sphingofungin E (2).