Divergent synthesis of (+)-tanikolide and its analogues employing stereoselective rhodium(II)-catalyzed reaction. Issue 10 (8th March 2018)

• Record Type: Journal Article
• Authors: Jinnouchi, Hikari; Nambu, Hisanori; Fujiwara, Tomoya; Yakura, Takayuki
• Is Part Of: Tetrahedron. Volume 74:Issue 10(2018)
• Page Start: 1059
• Page End: 1070
• Publication Date: 2018-03-08
• Subjects: Divergent synthesis -- Oxonium ylide -- Rearrangement -- Rhodium -- Lactonization; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tet.2018.01.035
• Languages: English
• ISSNs: 0040-4020

Abstract

Abstract: In this study, we described the divergent synthesis of (+)-tanikolide and its analogues, such as (4 S )- and (4 R )-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 tetrahydrofuran-5-methanol to γ-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. Graphical abstract: Highlights: The divergent synthesis of (+)-tanikolide and its analogues is described. Rh(II)-catalyzed reaction constructed the quaternary chiral center of tanokolides. This protocol provides high flexibility for the synthesis of a variety of analogues.