通过催化玻利化对的化
Carl W Liskey1, Xuebin Liao, John F Hartwig
1Department of Chemistry, University of Illinois, 600 South Matthews Avenue, Urbana, Illinois 61801-3602, USA.
Journal of the American Chemical Society
|August 4, 2010
概括
这项研究引入了一种单一的方法,用于用催化C-H化和铜介导化对的元化. 这种高效的工艺可以从各种芳香化合物中合成甲基替代的利利.
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:
- 烯烯是制药和材料科学中至关重要的构建模块.
- 将功能化导向到舞台的元位置仍然是一个合成的挑战.
- 现有的元化方法往往需要多步骤的程序或恶劣的条件.
研究的目的:
- 开发一种新的单方法,用于的甲化.
- 为了建立有效的条件,以铜为媒介的化甲基酸的和酸.
- 为了证明开发的合成元替代性利利的方法的广泛适用性.
主要方法:
- 一个电位的连续催化C-H化.
- 在in-situ生成的甲酸乙烯 Ester 的铜介导的化.
- 对化和化步骤的反应条件的优化.
主要成果:
- 从各种烯和异烯中成功合成了甲基替代的烯.
- 与包括化物,子, Ester,胺和受保护的酒精在内的多种功能组的兼容性得到证明.
- 有效地将受保护的转化为埃特拉维林合成的关键中间体.
- 进一步衍生元替代的酸到阿尔代,酸,胺,碳酸,四醇和胺.
结论:
- 开发的单方法提供了一种高效和多用途的途径,以获得元替代的利利.
- 这种方法简化了复杂芳香化合物的合成,具有潜在的制药应用.
- 报告的条件扩大了C-H功能化和化反应的范围.
相关概念视频
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.
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
Electrophilic Aromatic Substitution: Nitration of Benzene
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.


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