通过sp3-C-H功能化快速构建碳循环骨架:在内部氧化还原过程中,化物从一个异形的三级位置转移到一个化物
Keiji Mori1, Shosaku Sueoka, Takahiko Akiyama
1Department of Chemistry, Faculty of Science, Gakushuin University, Toshima-ku, Tokyo, Japan.
Journal of the American Chemical Society
|February 11, 2011
概括
这项研究引入了一种新的化学反应,用于创建复杂的分子. 它通过独特的化物转移和循环过程实现这一目标,使有机合成中的新途径成为可能.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 催化剂是一种催化剂.
背景情况:
- 化物转移在有机反应中至关重要.
- 开发新的CH功能化方法是一个关键的挑战.
- 对这些转换的阿利法,非基系统的探索较少.
研究的目的:
- 报告第一个非基化物转移/循环序列的非基化物.
- 为了展示新的sp(3)-C-H功能化策略.
- 为了合成四氨酸和氨酸衍生物.
主要方法:
- 使用一种新的[1,5]-化物转移/循环.
- 使用一种新的[1,6]-化物转移/循环.
- 在阿利法系统中研究sp(3) -C-H功能化.
主要成果:
- 成功构建了一个四线骨架.
- 形成五个成员的环 (印衍生物).
- 展示了两种不同类型的新型sp(3)-C-H功能化.
结论:
- 描述的序列代表了合成有机化学的重大进步.
- 这种方法为有价值的循环化合物提供了新的途径.
- 扩大了化物转移/循环反应的范围.
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.
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction mixture.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.

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