三醇-Au(I) 复合物:一种新型的催化剂,具有更好的热稳定性和反应性,用于分子间基胺化
Haifeng Duan1, Sujata Sengupta, Jeffrey L Petersen
1C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
Journal of the American Chemical Society
|August 7, 2009
概括
新的黄金 (I) 催化剂与三醇配体显示增强的热稳定性,并使具有挑战性的不反应基质的分子间胺化,使用较少的催化剂.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 合成化学 合成化学
背景情况:
- 金 ((I) 催化剂对于各种有机转化是有效的.
- 现有的黄金催化剂可能遭受有限的热稳定性.
- 水氨基化反应对于氨基的合成至关重要.
研究的目的:
- 为了合成和表征新的1,2,3-三醇结合的阴阳性黄金 (((I)) 催化剂.
- 为了评估这些新的黄金复合物的热稳定性和催化性能.
- 为了实现具有挑战性的分子间氨基化,使用不那么有反应性的基质.
主要方法:
- 金的合成和X射线晶体学 ((I) 复合物.
- 可变温度的核磁共振 (NMR) 光谱学.
- 对分子间胺化反应的催化试验.
主要成果:
- 新的1,2,3-三醇结合的阴阳性黄金 (((I) 催化剂成功合成和表征.
- 与现有的黄金催化剂相比,这些催化剂具有更高的热稳定性.
- 具有挑战性的与内部基和未受保护的阿里法氨基胺的分子间氨基化,在低催化剂负载下获得了优异的产量.
结论:
- 开发的黄金 (I) 催化剂提供了增强的热稳定性和催化活性.
- 这些催化剂为合成有价值的氨基化合物提供了有效的方法.
- 这些发现为在复杂有机合成中利用黄金催化剂开辟了新的途径.
相关概念视频
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.
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.
Preparation of 1° Amines: Azide Synthesis
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
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: Acid-Catalyzed Hydration
Introduction
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.
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.
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.


