光诱导的基因与N-基氧酸的碳amylarylation
Kohei Sekine1,2, Gaofan Yue2, June Kajiwara2
1Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen, Kasuga-shi, Fukuoka 816-8580, Japan.
这项研究引入了一种新的方法,用于使用可见光和N-aryl氧化酸去功能化alkynes. 该过程通过激素添加和aryl迁移机制高效地产生arylacrylamides.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 光催化作用的光催化
背景情况:
- 1,2-阿尔基因的功能失调为复杂的有机分子提供了直接途径.
- 在有机合成中,开发高效和原子经济的合成策略至关重要.
研究的目的:
- 开发一种可见光诱导的新型协议,用于终端基因的碳amylarylation.
- 为了利用N-氧胺酸作为易于获得的双功能试剂进行这种转化.
主要方法:
- 使用可见光光催化剂来启动反应.
- 在辐射下,终端基因与N-氧胺酸发生反应.
- 反应机制涉及碳基添加和随后的1,4-基迁移.
主要成果:
- 该研究成功地实现了终端基因的可见光诱导的碳amylarylation.
- 亚里亚烯胺被合成的产量中等到很高.
- 反应通过一种新的C(aryl) -N键裂解路径进行.
结论:
- 这项工作提出了一种高效和实用的合成阿里拉克利胺的方法.
- 开发的协议为合成化学家的基因功能化工具包提供了宝贵的补充.
- 可见光和双功能试剂的使用突出了对复杂分子合成的可持续方法.
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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.
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
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.
Alkynes to Carboxylic Acids: Oxidative Cleavage
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.
