一个高度刻板选择的,模块化路径到 (E) - 乙烯硫和 (Z) - 和 (E) - 基
Marie-Gabrielle Braun1, Béatrice Quiclet-Sire, Samir Z Zard
1Laboratoire de Synthèse Organique, CNRS UMR 7652, Ecole Polytechnique, 91128 Palaiseau, France.
Journal of the American Chemical Society
|September 20, 2011
概括
一种新的根基碎片方法从具有高立体选择性的合醇中产生乙烯硫. 这种方法使各种替代的合成成为可能,提供了一种多功能合成途径.
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:
- 醇是有机合成中的多功能前体.
- 类基因的立体选择性合成仍然是一个关键的挑战.
- 乙烯基硫是有价值的合成中间体.
研究的目的:
- 开发一种新的,高度刻板选择的路径到 (E) - 乙烯基硫.
- 为了利用合醇作为起始材料.
- 建立一个融合合成战略.
主要方法:
- 2--6-皮里迪诺基衍生物的根本碎片化.
- 乙烯基硫中间体的立体选择性形成.
- 后续的转化,如还原性脱硫化或催化合.
主要成果:
- 从醇中成功合成了 (E) - 乙硫.
- 在碎片化过程中实现的高立体选择性.
- 获取各种二-和三替代 (E) -和 (Z) -基.
结论:
- 极端碎片化为维尼尔硫提供了一个新的,高效的,立体选择性的途径.
- 这种方法为有价值的基构建块提供了一条融合的路线.
- 开发的战略扩大了烯合成的工具包.
相关概念视频
E2 Reaction: Stereochemistry and Regiochemistry
Elimination reactions of alkyl halides can yield one or more alkenes depending on the specific regiochemical and stereochemical considerations. While the regiochemistry of the reaction governs the location of the double bond in the product, the stereochemical requirements often influence the geometry.
When a substrate with two different β hydrogens undergoes an E2 elimination, the presence of a strong base can yield two regioisomeric alkenes. The more-substituted alkene is the major product and...
When a substrate with two different β hydrogens undergoes an E2 elimination, the presence of a strong base can yield two regioisomeric alkenes. The more-substituted alkene is the major product and...
E1 Reaction: Stereochemistry and Regiochemistry
One of the critical aspects of the E1 reaction mechanism, as also observed in E2, is the regiochemistry, with multiple regioisomers obtained as products. In the example discussed, the presence of water as a weak base favors elimination over substitution to generate two alkenes. Given that alkenes’ stability increases with the number of alkyl groups across the double bond, typically, E1 reactions lead to the Zaitsev product, for this is more substituted and stable than the Hofmann product.
Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
[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.
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.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.

