整体合成N-甲基二维丁丁氨酸 D 异尼铁
Vikram Bhat1, Kevin M Allan, Viresh H Rawal
1Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
Journal of the American Chemical Society
|March 31, 2011
概括
研究人员首次实现了N-methylwelwitindolinone D isonitrile的总合成,这是一个复杂的醇化物. 这一突破利用了新的方法来构建其复杂的bicyclo[4.3.1]decane核心并安装关键的功能组.
科学领域:
- 有机化学 有机化学
- 自然产品的合成自然产品的合成
- 药用化学 医学化学
背景情况:
- 印度醇化物代表着具有多样化生物活动的重要自然产品类.
- N-methylwelwitindolinone D isonitrile 是该家族的一个复杂成员,具有独特的双循环[4.3.1] 甲基核.
- 这种复杂的天然产品的总合成在有机化学中提出了重大挑战.
研究的目的:
- 开发一个简洁而高效的N-methylwelwitindolinone D isonitrile的总合成.
- 建立一种合成途径,以获取复杂的双环[4.3.1]含甲的醇化物.
- 证明关键化学转换的可行性,以构建天然产品的五环框架.
主要方法:
- 易斯酸介导的基化合用于快速的碳核心组装.
- 用Palladium催化酸乙烯酸化来构建核心结构.
- 印度尔氧化和循环,形成五环周期的最后一个环.
- 化物重新排列为异硫基亚酸盐,然后进行脱硫,以安装异二烯基组.
主要成果:
- 成功和简洁的N-甲基welwitindolinoneD isonitrile的总合成.
- 复杂的cyclo[4.3.1]decane碳核心的高效建设.
- 对这种类型的醇醇类化合物的新型合成策略的演示.
- 安装具有特征的异尼基功能组.
结论:
- 开发的合成途径提供了一种可行的方法,用于获取N-methylwelwitindolinone D isonitrile.
- 这种合成为制备类似物和相关复杂的醇类化合物开辟了道路.
- 这项研究强调了现代合成方法在天然产品合成中的力量.
相关概念视频
Nitrosation of Enols
The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
Preparation of Nitriles
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...
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.
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
The Wittig reaction is the conversion of carbonyl compounds-aldehydes and ketones-to alkenes using phosphorus ylides, or the Wittig reagent. The reaction was pioneered by Prof. Georg Wittig, for which he was awarded the Nobel Prize in Chemistry.
Nitriles to Ketones: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles react with a Grignard reagent, followed by an aqueous acid, to yield ketones. The reaction introduces a new carbon–carbon bond. The alkyl–magnesium bond in the Grignard reagent is highly polar, so the alkyl carbon develops a carbanionic character and acts as a nucleophile.
The mechanism begins with a nucleophilic attack by the Grignard reagent...
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
The Wittig reaction, which converts aldehydes or ketones to alkenes using phosphorus ylides, proceeds through a nucleophilic addition‒elimination process.
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...


