(E) -ビニルスルフォンおよび (Z) -および (E) -アルケネへの高度にステレオ選択的,モジュール型経路です
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
まとめ
新しい根本分裂法により,高いステレオ選択性を持つアリルアルコールからビニルスルフォンを生成します. このアプローチにより,様々な代用アルケンの合成が可能になり,汎用性の高い合成経路を提供します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 合成方法論 合成方法論
- ステレオセレクティブ合成
背景:
- アリルアルコールは,有機合成における汎用的な前駆体である.
- アルケンのステレオセレクティブ合成は,依然として重要な課題です.
- ビニル硫黄は,価値ある合成中介物質である.
研究 の 目的:
- (E) - ビニル硫黄への新しい,高度にステレオ選択的な経路を開発する.
- アリルアルコールを原料として利用する.
- 収束した合成戦略を確立する.
主な方法:
- 2-フッロロ-6-ピリジノキシ誘導体の根本的な断片化.
- ビニルスルフォン中間物質のステレオ選択的形成.
- 還元性脱硫ニル化やニッケル触媒結合などの後の変換.
主要な成果:
- アリルアルコールから (E) -ビニルスルフォンを合成した.
- 断片化プロセスで達成された高いステレオ選択性.
- 多種多様な二,三置換 (E) 及び (Z) 基へのアクセス.
結論:
- ラジカル・フラグメンテーションは,ビニルスルフォンへの新しい,効率的でステレオセレクティブな経路を提供します.
- この方法は,価値あるアルケンの構成要素に収束する経路を提供します.
- 策定された戦略は,アルケンの合成のためのツールキットを拡張します.
関連する概念動画
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.

