有机催化式的选性对合物添加到alkynones
Marco Bella1, Karl Anker Jørgensen
1Danish National Research Foundation: Center for Catalysis, Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark.
Journal of the American Chemical Society
|May 6, 2004
概括
这项研究引入了第一个对alkynones的β-dicarbonyl化合物的enantioselective催化添加. 开发的有机催化方法实现了高产量和优秀的性子产品的性选择性.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- β-二碳化合物是多功能合成构建块.
- 基是有机合成中有价值的迈克尔受体.
- 开发对联添加的酶选择性方法对于合成性分子至关重要.
研究的目的:
- 为了呈现第一个催化式的enantioselective联合添加β-dicarbonyl化合物到alkynones.
- 开发一个高效的一程序,以访问光学活性 (E) -enone adducts.
主要方法:
- 作为一种有机催化剂,利用了藻类化物[DHQ]2PHAL.
- 采用了两步,一个的催化系统,涉及[DHQ]2PHAL和微 (Bu3P).
- 研究了beta-dicarbonyl化合物和alkynones之间的合加法反应.
主要成果:
- 在联加法反应中取得了非常高的产量.
- 获得了 (Z) - 和 (E) -enones的混合物,其反体过量 (ee) 高达95%.
- 成功开发了一种单程序,产生光学活性 (E) -enone adducts.
结论:
- 开发的有机催化方法代表了不对称合成的重大进步.
- 单程序提供了一条有效的途径,以实现对抗聚合物丰富的 (E) -enones.
- 这种方法为合成复杂的性分子提供了强大的工具.
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Introduction to Electrophilic Addition Reactions of Alkenes
The double bond in a simple, unconjugated alkene is a region of high electron density that can act as a weak base or a nucleophile. The filled π orbital (HOMO) of the double bond can interact with the empty LUMO of an electrophile. A bonding interaction occurs when the electrophile attacks between the two carbons; the electrophile then accepts a pair of electrons from the π bond and undergoes addition across the double bond, yielding a single product.
Addition and elimination reactions can be...
Addition and elimination reactions can be...
Preparation of Alkynes: Alkylation Reaction
Introduction
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.
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.
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
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.
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
Introduction
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.
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.
Conjugate Addition to α,β-Unsaturated Carbonyl Compounds
α,β-Unsaturated carbonyl compounds are molecules bearing a carbonyl and alkene functionality in conjugation with each other. The conjugation in the molecule leads to three resonance structures. The hybrid form exhibits two probable electrophilic sites: the carbonyl carbon and the β carbon.


