Divergent synthesis of (+)-tanikolide and its analogues employing stereoselective rhodium(II)-catalyzed reaction

TETRAHEDRON

卷:74

Article

Jinnouchi, Hikari¹  Nambu, Hisanori¹  Fujiwara, Tomoya¹  Yakura, Takayuki¹ 

[1] Univ Toyama, Grad Sch Med & Pharmaceut Sci, Sugitani, Toyama 9300194, Japan

关键词: Divergent synthesis;    Oxonium ylide;    Rearrangement;    Rhodium;    Lactonization;   

DOI  :  10.1016/j.tet.2018.01.035

来源: Elsevier

【 摘 要 】

In this study, we described the divergent synthesis of (+)-tanikolide and its analogues, such as (4S)- and (4R)-hydroxytanikolides, and nortanikolide, employing a stereoselective dirhodium(II)-catalyzed reaction to construct the quaternary chiral center of tanokolides. The key steps involve (a) a dirhodium(II)-catalyzed oxonium ylide formation-[2,3]-sigmatropic rearrangement, (b) an N-heterocyclic carbene-catalyzed ring-expansion lactonization of tetrahydrofurfural, or (c) an oxidative cleavage of tetrahy-drofuran-5-methanol to gamma-lactone using a 2-iodobenzamide catalyst. This route would provide high flexibility for analogue synthesis because the long side chain can be introduced at a later stage in the synthesis. (C) 2018 Elsevier Ltd. All rights reserved.

【 授权许可】

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