一合成终端基因从基因
Cristina Bilanin1, Amravati S Singh1, Lluis Martínez-Belenguer1
1Instituto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València-Agencia Estatal Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022 Valencia, Spain.
从基中合成终端基因现在更简单了. 一种新的一方法使用催化和温和条件将基转化为有价值的基,包括乙.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 从基中直接合成终端基因是有机合成的一个重大挑战.
- 现有的方法通常需要恶劣的条件或特殊的试剂.
研究的目的:
- 开发一种新,高效和温和的单方法,直接从终端基中合成终端基.
- 通过使用易于获得的原料,提供一种直接通往有价值的基化合物的途径.
主要方法:
- 一个两步一的过程,涉及到终端基的化催化脱化水化.
- 由此产生的乙烯基锡兰中间体的氧化脱,使用利胺 (III) 二氧化三乙酸 (PhIO) 和三化物 (BF3).
主要成果:
- 成功地将各种基和芳香终端基转化为相应的终端基.
- 反应在温和条件下进行,并使用商用试剂.
- 该方法提供了高效率的终端基,包括乙.
结论:
- 开发的方法提供了一种实用而简单的方法,用于从基中直接合成终端基.
- 这种方法扩大了合成工具箱,以获取有机化学中重要的基构建块.
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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.
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.
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.
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.
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.
