催化式脱碳添加法胺到基的脱碳添加
Yuichi Kajita1, Seijiro Matsubara, Takuya Kurahashi
1Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
一种新的催化反应使N-甲胺和基能够形成替代的异类. 该机制涉及Ni(0) 催化剂对胺键的核友攻击,启动催化循环.
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:
- 聚胺衍生物是药物化学中的重要支架.
- 开发高效的合成路径到异诺结构具有显著的兴趣.
- 催化为C-N和C-C键形成提供了一个多功能平台.
研究的目的:
- 开发一种新的分子间催化加法反应.
- 从易于获得的N-arylphthalimides和alkynes中合成替代性异诺.
- 为了阐明观察到的转换的机械路径.
主要方法:
- 在N-arylphthalimides和各种基之间发生分子间反应.
- (0) 催化剂系统.催化剂系统.
- 反应条件的优化 (催化剂负载,溶剂,温度).
- 机理学研究包括同位素标记和计算分析 (建议).
主要成果:
- 成功合成多种替代性异诺.
- 观察到高产量和良好的功能性群体耐受性.
- 提出了一个可信的催化循环,由Ni{0}对胺的核友攻击启动.
结论:
- 已经建立了一种新的,高效的催化合成途径,以替代异诺.
- 这种反应可以从简单的原料中获得有价值的异环化合物.
- 拟议的机制提供了对介导胺激活和基内插入的见解.
更多相关视频
11:44Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
12:07Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
相关概念视频
Electrophilic Addition to Alkynes: Halogenation
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.
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.
Electrophilic Addition to Alkynes: Hydrohalogenation
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.
