The first total synthesis and reassignment of the relative stereochemistry of 16-hydroxy-16,22-dihydroapparicine

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• 作者：Yoshihiko Noguchi ; Tomoyasu Hirose ; Yujiro Furuya ; Aki Ishiyama ; Kazuhiko Otoguro ; Satoshi 艑mura ; ^{omuras@insti.kitasato-u.ac.jp} ; Toshiaki Sunazuka ; ^{sunazuka@lisci.kitasato-u.ac.jp}
• 关键词：Apparicines ; Total synthesis ; Cascade reaction ; Stereospecific 1 ; 2-addition ; Relative stereochemistry
• 刊名：Tetrahedron Letters
• 出版年：2012
• 期刊代码：109_00404039
• 类别：ch
• 出版时间：4 April, 2012
• 卷：53
• 期：14
• 页码：1802-1807
• 文件大小：712 K

摘要

We report the first total synthesis and reassignment of the relative stereochemistry of naturally occurring 16-hydroxy-16,22-dihydroapparicine. Our novel route proceeds by a cascade reaction to efficiently construct a 1-azabicyclo[4.2.2]decane core, along with two stereocenters (C-15 and C-16). The C-16 quaternary carbon was constructed through stereospecific 1,2-addition using an indole nucleophile to an aldehyde or a methylketone. The stereospecific synthesis of two diastereomers of the target product has revealed the true relative stereochemistry of the natural compound.