从1-alkynes,aldehydes和morpholine中合成1,3-非替代的艾伦的一合成
1Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, 3663 North Zhongshan Lu, Shanghai 200062, PR China.
酸 (ZnI2) 催化了一步合成从和化物中生成的烯. 这种高效的方法可以容忍各种功能组,为烯化合物提供了一条多功能途径.
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:
- 艾伦是有价值的合成中间体,具有多样化的应用.
- 在有机化学中,对烯合成的高效和选择性方法非常受欢迎.
- 以前的合成路线通常需要多个步骤或恶劣的条件.
研究的目的:
- 开发一种新的,单步的催化方法来合成阿伦基因.
- 调查化 (ZnI2) 作为这种转变的有效催化剂的使用.
- 为了探索与各种化物和化物的反应的范围和局限性.
主要方法:
- 终端基因与化物在酸 (ZnI2) 催化剂和形态基的存在下的一步反应.
- 溶剂:多烯. 溶剂:多烯. 溶剂:烯.
- 拟议的反应机制涉及Propargylic氨基中间体,经过化物转移和β-消除.
主要成果:
- 在单个步骤中成功合成阿伦.
- 这种反应对芳香性和性化物都有效.
- 耐受各种功能组,包括化物,基和氨基.
结论:
- 二氧化 (ZnI2) 是一种有效的催化剂,用于单步合成烯.
- 开发的方法提供了一种多功能和功能组耐受性路径,可用于allenes.
- 涉及propargylic amines的拟议机制为反应途径提供了洞察力.
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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.
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.
Amines to Alkenes: Hofmann Elimination
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
