1,2-金属酸盐重组作为合成合醇的工具箱
Yannick Linne1, Daniel Lohrberg1, Henry Struwe1
1Institute of Organic Chemistry, Gottfried Wilhelm Leibniz Universität Hannover, 30167 Hannover, Germany.
The Journal of organic chemistry
|August 18, 2023
概括
研究人员提出了一种使用1,2-金属酸盐重组合成合醇的新方法,为Nozaki-Hiyama-Takai-Kishi反应提供了替代方案. 这种方法成功地构建了两个单基,证明了其在有机合成中的实用性.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 醇是生物活性物质中特权的结构动图.
- 诺扎基 - 希山 - 塔卡伊 - 基希反应是当前合成醇醇的标准.
研究的目的:
- 开发一种有价值的替代方法来合成基醇.
- 为了探索在霍普-马特森-阿格瓦尔反应中使用乙烯基酸乙的应用.
主要方法:
- 使用一个1,2-金属重组策略.
- 使用霍普-马特森-阿格瓦尔反应与各种乙烯基乙烯基 Ester.
- 应用一个融合合成策略.
主要成果:
- 证明了对现有的醇合成方法的可行替代方案.
- 通过使用具有多种功能组的乙烯基烯酸 Ester 成功合成了合醇.
- 使用这种新的合成方法制造了两个单体体.
结论:
- 1,2-金属酸盐重组为合醇合成提供了一个强大的替代方案.
- 霍普-马特森-阿格瓦尔反应在功能化的乙烯基乙烯基 Ester 中是有效的.
- 这种融合策略适用于构建复杂的自然产品,如单类.
相关概念视频
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
2.2K
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
2.2K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.5K
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.
8.5K
Acid Halides to Alcohols: Grignard Reaction
2.3K
Organomagnesium halides, commonly known as Grignard reagents, convert acid halides to tertiary alcohols. The reaction requires two equivalents of the Grignard reagent and proceeds via a ketone intermediate.
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
2.3K
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
3.4K
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
3.4K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
3.8K
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...
3.8K


