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 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.
2-ジアゾ-3-ケトエステルの化学・立体選択的ロジウム(II)触媒オキソニウム イリド形成-[2,3]-シグマトロピー転位反応を基軸とする天然物 (+)-tanikolide および類縁体の全合成 (Total synthesis of (+)-tanikolide and its analogues based on novel chemoand stereoselective rhodium(II)-catalyzed oxonium ylide formation-[2,3]sigmatropic rearrangement of 2-diazo-3-ketoesters)
The total synthesis of (+)-tanikolide was accomplished by a traceless stereoinduction method using the key steps of a Rh(II)-catalyzed oxonium ylide formation-[2,3]-sigmatropic rearrangement and an N-heterocyclic carbene-catalyzed ring-expansion lactonization of tetrahydrofurfural. This synthetic route is applicable to the divergent synthesis of tanikolide analogues.
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