光化学转移到基因通过选择性基化
Amit Pal1, Prakash Maity1, Fathima Niloofar1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala PO, Vithura, Thiruvananthapuram, Kerala 695551, India.
这项研究引入了一种新型的光化学方法,用于从基中合成不和硫. 该工艺利用1,4-DHP硫替代物,提供了一条通往有价值化学化合物的多功能途径.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 催化剂是一种催化剂.
背景情况:
- 碳酸化是合成硫的关键转化.
- 开发高效和选择性的甲化方法仍然是一个活跃的研究领域.
- 光化学方法在有机合成中提供了独特的反应途径.
研究的目的:
- 报告第一个使用1,4-DHP硫替代物的基因的基化.
- 为了建立一个通用的光化学路径到 (E) -和 (Z) -α,β-不和铁.
- 开发一种用于高效和选择性硫合成的催化系统.
主要方法:
- 使用稳定的1,4-DHP硫替代品.
- 采用光化学条件进行反应.
- 开发一种用于激活和碳化的/光氧化催化系统.
- 使用基和基易斯酸对进行E-to-Z光异构化.
主要成果:
- 首次实现了 (未) 激活的基的基化.
- 产生了一条通往具有高区域和立体选择性的 (E) -α,β-不和乙的通路.
- 通过E-到-Z光异构化成功访问了 (Z) -α,β-不和硫乙.
- 使用Pd/photoredox系统,对光异构和副作用的控制得到了证明.
结论:
- 开发的光化学方法提供了一种多功能和选择性的途径,可以获得α,β-不和硫.
- 在光化学条件下使用1,4-DHP硫替代物对基化有效.
- 催化系统可以控制立体化学,允许访问E和Z同位素.
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相关概念视频
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Electrophilic Addition to Alkynes: Hydrohalogenation
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Preparation and Reactions of Thiols
