用铜催化终端基因的基化
Mycah R Uehling1, Alison M Suess, Gojko Lalic
1The Department of Chemistry, University of Washington , Seattle, Washington 98195, United States.
一种新的铜催化反应有效地从终端基和基三酸盐中合成 (E) 基. 这种基化方法提供了出色的区域选择性和功能组耐受性,使得二极 stereospecific 基的形成.
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:
- 烯合成在有机化学中至关重要.
- 开发有效和选择性的方法来制造特定的异构体仍然是一个活跃的研究领域.
- 铜催化为各种有机转化提供了一个多功能平台.
研究的目的:
- 为开发一种新的铜催化基化反应.
- 为了利用终端基和基三酸盐合成 (E) -基.
- 在基化过程中实现高区域选择性和功能组耐受性.
主要方法:
- 铜催化基化反应.
- 基三酸盐作为基化剂的使用.
- 使用六甲基二氧化作为化物来源.
- 用各种和三酸盐进行基质范围勘探.
主要成果:
- 具有优异的反马尔科夫尼科夫的区域选择性 (anti-Markovnikov regioselectivity) 的 (E) - 基独有的形成.
- 对基和基替代基的成功应用.
- 与初级基和基三酸盐的兼容性.
- 在反应过程中对广泛的功能群的耐受性.
结论:
- 已经建立了一种高效和异体特定的合成 (E) - 基的方法.
- 反应提供了一个有价值的路线,从易于获得的原材料.
- 一个拟议的机制涉及铜化物形成,化和铜中间体的化.
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相关概念视频
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.
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.
Electrophilic Addition to Alkynes: Hydrohalogenation
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.
