摄影氧催化多元件α-硫化终端基因
Mingyue Zheng1, Xin Zhuang1, Qianfa Jia2
1Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, P. R. China.
这项研究引入了一种创建复杂分子的新方法. 它使用光来有效地连接简单的构建块,形成具有多样性结构的有价值的化合物.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 合成化学 合成化学
背景情况:
- 硫化反应在有机合成中至关重要.
- 开发高效和选择性的α-硫化方法仍然是一个挑战.
研究的目的:
- 探索一种以泛性为导向的和适应性的基因α-硫化.
- 开发一种光诱导的多组件激进交叉合策略.
主要方法:
- 使用的终端基,硫酸盐和酒精/基/基.
- 采用光诱导的根性交叉合.
- 研究了轻度反应条件和功能组耐受性.
主要成果:
- 成功实现了基因的α-硫化.
- 证明了广泛的基质范围和出色的选择性 (化疗,部位和立体).
- 在后期阶段的功能化中展示了适用性.
结论:
- 开发了一个模块化平台,用于合成含α-硫的多替代基.
- 该协议从简单的前体提供了一种多功能方法.
- 突出了创造增值,结构多样化的化合物的潜力.
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相关概念视频
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: 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.
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 of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
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.
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
