不对称的双重组合有趣的重新安排/阿尔多尔反应
Natalie C Giampietro1, Jeff W Kampf, John P Wolfe
1Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
Journal of the American Chemical Society
|August 15, 2009
概括
一种新的非对称合成方法可以创建具有高立体控制的复杂二基. 这种技术可以有效地产生基丰富的化合物,包括抗真菌剂的中间体.
科学领域:
- 有机化学 有机化学
- 不对称的合成方法
- 立体选择性反应
背景情况:
- 状辅助器对于立体控制合成至关重要.
- 在有机合成中,开发高效的合成α,β-二基的方法非常重要.
- 四季度立体中心带来了合成的挑战.
研究的目的:
- 开发一种新的非对称合成α--α,β-dihydroxy .
- 构建两个C-C键和两个立体中心,包括一个四元中心.
- 为了证明这种方法在合成替代酸的关键中间体中的实用性.
主要方法:
- 双重维蒂格重组/阿尔多尔反应的O-基或O-基糖醇.
- 使用来自2-环醇的性辅助剂.
- 基拉辅助体的裂变,以获得聚富的产品.
主要成果:
- 成功合成阿尔法-基-阿尔法,β-二基乙的不对称合成.
- 建造两个立体中心,一个四级,具有出色的立体控制 (syn diols).
- 以高达95%的EE获得的以反聚物丰富的产品.
- 在合成替代酸的关键中间体中证明了应用.
结论:
- 描述的双重反应序列是不对称合成的有效方法.
- 这种方法提供了出色的立体控制,产生合成产品.
- 这种方法对于制备基丰富化合物和复杂中间体非常有价值.
相关概念视频
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...
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.
Crossed Aldol Reactions: Overview
Crossed aldol addition is the reaction between two different carbonyl compounds under acidic or basic conditions. Here, both the carbonyl compounds function as nucleophiles and electrophiles. As shown in Figure 1, such a reaction yields a mixture of products, two of which are formed via self-condensation, while the remaining two are formed via crossed-condensation. Without adjustment, the reaction's usefulness in organic chemistry is decreased.
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.
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
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.
Crossed Aldol Reaction Using Strong Bases: Directed Aldol Reaction
The reaction between two different carbonyl compounds comprising α hydrogen in the presence of a strong base like lithium diisopropylamide (LDA) to form a crossed aldol product is known as a directed aldol reaction. The directed aldol reaction is depicted in Figure 1.


