ベンザヌレーション/オキノンメチド形成/電循環カスケードによる両方のクロメンのリングの同時合成
Nilanjana Majumdar1, Keith A Korthals, William D Wulff
1Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA.
Journal of the American Chemical Society
|December 20, 2011
まとめ
研究者は,クロメンのための新しいクロム触媒合成を開発し,両方のリングを1つのステップで形成しました. この効率的な方法は,フィッシャーカルベン複合体とプロパルギルエーテルを使用し,ラパケノールやビタミンEなどの貴重な化合物へのアクセスを可能にします.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 合成化学 合成化学とは
背景:
- クロメン誘導体は,多様な生物学的活動を持つ重要なヘテロサイクリック化合物です.
- クロメンへの既存の合成経路は,しばしば複数のステップと厳しい条件を必要とします.
研究 の 目的:
- クロメンリングシステムのための新しい,効率的で1段階の合成を開発する.
- 生物学的に重要な分子を合成するためのこの新しい方法の有用性を探求する.
主な方法:
- クロミウムのα,β不飽和フィッシャーカルベンの複合体と機能化されたプロパルギルエーサーの反応.
- ベンザヌレーション,オキノンメチド形成,電循環を含むカスケード反応.
主要な成果:
- クロメン環系への新しい合成経路が成功裏に確立されました.
- 反応はカスケードメカニズムを経て進み,単一の合成操作で両方のリングを生成します.
- この方法は,ラパケノールとビタミンEの合成に適用されました.
結論:
- この研究は,両方のリングが同時に形成されるクロメンの最初のシングルステップ合成を提示しています.
- 開発された方法は,代替クロメンおよび関連する天然製品にアクセスするための効率的な経路を提供します.
関連する概念動画
Preparation of Epoxides
Overview
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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...
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.


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