通过甲基的形式脱合成甲基
Riley A Roberts1, Bryan E Metze1, Aleksandra Nilova1
1Department of Chemistry, Portland State University, Portland, Oregon 97201, United States.
研究人员开发了一种新的两步方法, 这种方法提供了一种更温和,更有效的方法来获取这些用于药物和材料合成的多功能化学中间体.
科学领域:
- 有机化学
- 合成化学
背景情况:
- 类是合成药品,农业化学品和液晶中使用的各种类化合物的高能中间体.
- 目前生成的方法通常需要苛刻的条件或多步合成,这限制了它们的实际应用.
- 需要更精简和更温和的合成途径来获得易于获得的前体.
研究的目的:
- 开发一种新的两步形式脱方法,从简单的中产生.
- 能够在远离传统反应组的位置合成.
- 提供一种更高效,更耐受功能组的替代现有基生成技术.
主要方法:
- 采用了简单的两步正式脱.
- 区域选择性安装和随后的"离子"脱落组促进了的产生.
- 该方法与一系列简单的 (20个例子) 和类动物 (8个例子) 的兼容性得到了证明.
主要成果:
- 这种新的方法成功地在温和的条件下从简单的中产生了.
- 与当前最先进的 aryne 前体相比,该方法显示出更高的功能组耐受性和效率.
- 用于区域选择性C-H氨基化而生成的aryne中间体,表现出明显的反应模式.
结论:
- 开发的两步形式脱提供了一个有效和温和的途径从简单的.
- 这种方法扩大了arynes的合成效用,特别是在需要高功能组容忍的应用中.
- 这种方法为区域选择性C-H功能化提供了新的机会,与现有的方法不同.
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相关概念视频
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.
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.
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 Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes
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.
