通过银介导的三甲氧化的阿里尔斯坦南和阿里尔酸
Chenghong Huang1, Theresa Liang, Shinji Harada
1Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States.
Journal of the American Chemical Society
|August 11, 2011
概括
一种新的白银催化反应从酸和酸中产生三甲基乙烯. 这是第一种过渡金属催化方法,用于形成C () -OCF () (3) 键.
科学领域:
- 有机化学 有机化学
- 有机金属化学 有机金属化学
背景情况:
- 三甲基乙烯是药品和材料科学中重要的结构动图.
- 合成C ((aryl) -OCF ((3) 键的直接方法仍然具有挑战性.
研究的目的:
- 开发一种新型的过渡金属催化方法,用于合成三甲基乙.
- 为了建立一个新的路线,C(aryl) -OCF(3) 债券形成.
主要方法:
- 银介导的交叉合反应.银介导的交叉合反应.
- 作为合伙伴,使用了烯和烯酸.
- 使用三甲氧化物作为三甲氧化剂.
主要成果:
- 成功合成了三甲基乙.
- 证明了第一个过渡金属催化C ((aryl) -OCF ((3) 键的形成.
- 反应通过银介导的途径进行.
结论:
- 开发了一种高效的白银催化交叉合,用于三甲基乙醇合成.
- 这项工作为获取有价值的有机化合物提供了一个新的合成策略.
- 该方法为C(aryl) -OCF(3) 债券构造提供了一种新的方法.
相关概念视频
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.
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
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.
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
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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.


