从终端基和它们的合成实用品中制备替代的基衍生物
John R DeBergh1, Kathleen M Spivey, Joseph M Ready
1Department of Biochemistry, University of Texas Southwestern Medical Center at Dallas, Dallas, Texas 75390-9038, USA.
Journal of the American Chemical Society
|June 4, 2008
概括
这项研究引入了一种新方法,用于从终端基因中创建立体定义的基衍生物,使用双重碳金属化/氧化过程. 这种多功能反应可以合成有价值的中间体,用于复杂的分子构造.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 终端基是有机合成中的多功能构建块.
- 乙醇衍生物的立体选择性合成对于构建复杂分子至关重要.
研究的目的:
- 开发一种新的方法,从终端基中制备立体定义的基衍生物.
- 为了证明这种方法在合成有价值的有机化合物的实用性.
主要方法:
- 终端基的Cp2ZrCl2催化甲基发光.
- 维尼拉兰与过氧物种的氧化,形成三替代的酸盐.
- 用碳氧化无水化物或西三酸盐对乙烯酸盐进行电友性捕获.
主要成果:
- 成功合成立体定义的三替代醇和西兰酸盐.
- 证明了对各种功能组的耐受性,包括酒精,异环,烯酸和烯酸.
- 在昆虫フェロモン前列素 (frontalin) 的 enantioselective 合成中的应用.
- 将α-基化物转化为有价值的产品,通过同质化,还原性氨化,氧化和化.
结论:
- 开发的双重碳金属化/氧化策略提供了对立体定义的乙醇衍生物的有效访问.
- 这种方法为合成复杂的有机分子和自然产品提供了强大的工具.
- 进一步探索双重碳金属化/氨化反应的研究表明,合成恩-素的可能性很大.
相关概念视频
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.
Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction
α-Substituted ketones or aldehydes can be synthesized from enamines by the Stork enamine reaction, named after its pioneer Gilbert Stork. Enamines are useful synthetic intermediates where the lone pair on nitrogen is in conjugation with the C=C bond. They resemble enolate ions, as the resonance forms of both species have a nucleophilic α carbon.
Preparation of Alkynes: Dehydrohalogenation
Introduction
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.
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.
Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes
Aldehydes and ketones are prepared from alcohols, alkenes, and alkynes via different reaction pathways. Alcohols are the most commonly used substrates for synthesizing aldehydes and ketones. The conversion of alcohol to aldehyde, which involves the oxidation process, depends on the class of the alcohol used and the strength of the oxidizing agent. For instance, primary alcohol will form an aldehyde when treated with a weak oxidizing agent; however, it gets over-oxidized to a carboxylic acid in...
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an alkylated β-keto acid.
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.


