2023 Fiscal Year Final Research Report
Divergent synthesis of unsymmetrical polysulfides by the selective activation of sulfur-bonded leaving groups
| Project/Area Number |
22K14687
|
|---|
| Research Category |
Grant-in-Aid for Early-Career Scientists
|
| Allocation Type | Multi-year Fund |
|---|
| Review Section |
Basic Section 33020:Synthetic organic chemistry-related
|
|---|
| Research Institution | Tohoku University |
|---|
Principal Investigator |
|
|---|
| Project Period (FY) |
2022-04-01 – 2024-03-31
|
| Keywords | ジスルフィド / 多様性合成 / 脱離基 / アミノ基 / イミド基 / トリフルオロ酢酸 / アリルシラン / 芳香族求電子置換反応 |
|---|
| Outline of Final Research Achievements |
Disulfide bonds are prevalent in diverse fields, including medicinal chemistry, food chemistry, and materials science. Despite their wide applications, the synthesis of unsymmetrical disulfides is challenging because conventional methods tend to provide a mixture of symmetrical and unsymmetrical disulfides. To address this issue, we developed a new bilateral disulfurating reagent, N-(morpholine-4-dithio)phthalimide. This reagent has amino and imide leaving groups that can be orthogonally transformed. Under acidic conditions, the amino leaving group undergoes selective protonation and thus can be displaced by various carbon nucleophiles, such as allyl trimethylsilanes, alkynyl silanes, and electron-rich arenes. Meanwhile, the remaining phthalimide moiety is substituted by amines, thiols, and azlactones under basic or neutral conditions. The combination of these transformations provides access to diverse unsymmetrical disulfides through two C－S bond-forming reactions.
|
| Free Research Field |
有機合成化学
|
| Academic Significance and Societal Importance of the Research Achievements |
ジスルフィド化合物は，多彩な生物活性天然物に含まれることに加え，環状ペプチドの構築，機能性ポリマーやリチウム電池電極への利用など，様々な応用研究が期待される有用な化合物群である．その一方で，置換基導入の選択性の低さや，置換基のスクランブルなどにより，非対称なジスルフィドの精密合成は困難であった．本研究課題で開発した手法は，独自に開発したジスルフィドプラットフォーム分子の両側に多彩な置換基を選択的に導入できることから，自在な置換基の組み合わせを有する非対称ジスルフィドの短段階精密合成を可能とし，上記の応用研究を強く後押しするものと期待される．
|
