Stereoselective Synthesis of Homochiral Substituted Tetrahydrothiophenes by Electrophile-Promoted Thioetherification

Jana, Gourhari; Viso, Antonio; Dı́az, Yolanda; Castillón, Sergio

doi:10.1002/1099-0690(200301)2003:1<209::aid-ejoc209>3.0.co;2-s

“…Similarly, ( R )-glycidol was converted into the ( R )-enantiomer of 219 , eventually taken to thiofuranose analogues in the l -series. Differently protected unsaturated sulfanyl alcohol derivatives have been exploited as precursors of chiral tetrahydrothiophene compounds via electrophile-promoted thioetherification …”

Section: Synthesis Of Chiral Nonracemic Dihydro- and Tetrahydrothioph...mentioning

confidence: 99%

Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

Benetti

¹

,

Risi²,

Pollini³

et al. 2012

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“…License: CC BY-NC-ND 4.0 halocyclization of alkenoic thioester has only been reported once, albeit with an almost negligible (4%) yield of the desired product. 11 An alternative method for preparing cyclic sulfides that involves sulfenyl halides has also been used to synthesize prostaglandins. 12 Herein, we investigated the halocyclization of unsaturated thioesters and further conversion of the products obtained as a new protocol for the synthesis of S-heterocycles (Scheme 1B).…”

Section: Introductionmentioning

confidence: 99%

Bromocyclization of Unsaturated Thioester and Access to Functionalized Sulfur-heterocycles

Saegusa,

Fujihara,

Shigehisa

2023

Preprint

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The alkene halocyclization reaction is a significant synthetic organic chemical transformation, especially for the versatile synthesis of heterocycles. Although oxygen, nitrogen, and carbon have been extensively studied as nucleophilic elements in this transformation, sulfur-based nucleophiles are relatively unexplored. This is particularly intriguing given the prevalence of S-heterocycle- containing bioactive natural products. In this study, we investigated halocyclization chemistry involving unsaturated thioesters, with a focus on their use as potential S-nucleophiles. Despite their electron-withdrawing nature, thioesters are greater nucleophile rather than sulfides according to our previous study, which encouraged us to consider thioesters as viable halocyclization candidates. Thioesters, which are readily synthesized from alcohols or alkyl halides, are convenient starting materials. Here, we developed a novel bromocyclization method that uses alkenoic thioesters and N-bromoacetamide (NBA) to form cyclic bromosulfides. The resulting 5-exo products are labile and can be used in various nucleophilic substitution reactions. Furthermore, the reaction pathways involving bromonium intermediates and the HBr-promoted auto-activation of NBA were revealed by DFT calculations. This study provides new avenues for the synthesis of S-heterocyclic scaffolds and a pathway for future investigations into asymmetric variants with the aim of developing effective catalysts.

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“…License: CC BY-NC-ND 4.0 halocyclization of alkenoic thioester has only been reported once, albeit with an almost negligible (4%) yield of the desired product. 11 An alternative method for preparing cyclic sulfides that involves sulfenyl halides has also been used to synthesize prostaglandins. 12 Herein, we investigated the halocyclization of unsaturated thioesters and further conversion of the products obtained as a new protocol for the synthesis of S-heterocycles (Scheme 1B).…”

Section: Introductionmentioning

confidence: 99%

Bromocyclization of Unsaturated Thioester and Access to Functionalized Sulfur-heterocycles

Saegusa,

Fujihara,

Shigehisa

2023

Preprint

0

View full text Add to dashboard Cite

The alkene halocyclization reaction is a significant synthetic organic chemical transformation, especially for the versatile synthesis of heterocycles. Although oxygen, nitrogen, and carbon have been extensively studied as nucleophilic elements in this transformation, sulfur-based nucleophiles are relatively unexplored. This is particularly intriguing given the prevalence of S-heterocycle- containing bioactive natural products. In this study, we investigated halocyclization chemistry involving unsaturated thioesters, with a focus on their use as potential S-nucleophiles. Despite their electron-withdrawing nature, thioesters are greater nucleophile rather than sulfides according to our previous study, which encouraged us to consider thioesters as viable halocyclization candidates. Thioesters, which are readily synthesized from alcohols or alkyl halides, are convenient starting materials. Here, we developed a novel bromocyclization method that uses alkenoic thioesters and N-bromoacetamide (NBA) to form cyclic bromosulfides. The resulting 5-exo products are labile and can be used in various nucleophilic substitution reactions. Furthermore, the reaction pathways involving bromonium intermediates and the HBr-promoted auto-activation of NBA were revealed by DFT calculations. This study provides new avenues for the synthesis of S-heterocyclic scaffolds and a pathway for future investigations into asymmetric variants with the aim of developing effective catalysts.

show abstract

Stereoselective Synthesis of Homochiral Substituted Tetrahydrothiophenes by Electrophile-Promoted Thioetherification

Cited by 17 publications

References 10 publications

Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

Bromocyclization of Unsaturated Thioester and Access to Functionalized Sulfur-heterocycles

Bromocyclization of Unsaturated Thioester and Access to Functionalized Sulfur-heterocycles

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