阿尔德的同样基化和同样基化
1Department of Chemistry MS 015, Brandeis University, Waltham, Massachusetts 02454-9110, USA.
Journal of the American Chemical Society
|October 22, 2011
概括
一种新的循环酸基化方法有效地将同质基碎片添加到化物中,产生双基基基醇. 这种反应为甲基替代产品提供了高的立体选择性,在有机合成中很有用.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 立体选择性合成 立体选择性合成
背景情况:
- 合物的功能化在有机合成中至关重要.
- 开发有效的方法来创建复杂的酒精结构仍然是一个关键的挑战.
研究的目的:
- 描述一种新的方法,用于将同质碎片添加到化物中.
- 为了研究这种反应的立体化学结果.
主要方法:
- 使用环烯酸酸基化试剂.
- 在二 (PhBCl2) 的存在下,将这些试剂与化物发生反应.
- 使用光学活性起始材料来评估反选择性.
主要成果:
- 获得了高产量的双醇.
- 循环胺含的 cis-和 trans-crotyl 试剂有选择性地产生了 1,3-anti-和 1,3-syn-methyl 替代醇.
- 从光学活性反应剂中取代E的产品观察到优异的反体比率 (97:3er).
结论:
- 开发的方法提供了一个简单的途径,以 bishomoallyl alcohols.
- 反应过程具有很高的二选择性和反选择性,与齐默尔曼-特拉克斯勒过渡状态相一致.
- 这种方法扩大了复杂有机分子立体选择性合成的工具包.
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.
Aldehydes and Ketones with Alcohols: Hemiacetal Formation
Similar to water, alcohols can add to the carbonyl carbon of the aldehydes and ketones. The addition of one molecule of alcohol to the carbonyl compound forms the hemiacetal or half acetal. As depicted below, in a hemiacetal, the carbon is directly linked to an OH and OR group.
C–C Bond Formation: Aldol Condensation Overview
Aldol condensation is an important route in synthetic organic chemistry used to generate a new carbon–carbon bond under basic or acidic conditions. The aldol condensation reaction presented in Figure 1 constitutes an aldol addition reaction followed by the dehydration process.
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
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...
Base-Catalyzed Aldol Addition Reaction
As depicted in Figure 1, base-catalyzed aldol addition involves adding two carbonyl compounds in aqueous sodium hydroxide to form a β-hydroxy carbonyl compound.


