活性化されていない sp3 C-H 結合でアミド誘導光還元触媒による C-C 結合形成
John C K Chu1, Tomislav Rovis1,2
1Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
Nature
|October 13, 2016
まとめ
研究者らは,無活性な炭素-水素結合を選択的に活性化することによって,炭素-炭素結合形成のための新しい方法を開発しました. この戦略により,従来の方法では入手できない複雑な分子の合成が可能になり,より効率的な化学合成の道を開きます.
科学分野:
- 有機化学
- 合成化学
- カタリシス
背景:
- 炭素-炭素 (C-C) 結合の形成は,生物学的に重要な分子,材料,化学物質を合成するために不可欠です.
- 従来のC−C結合形成には,既存の機能群が必要で,合成のアクセシビリティは制限される.
- 惰性炭素-水素 (C-H) 結合の機能化は,新しい分子構造と効率的な合成への経路を提供します.
研究 の 目的:
- 非反応性C−H結合の誘導割れによるC−C結合形成のための新しい方法論を開発する.
- 複合分子内の活性化されていない sp3 C-H結合で選択的なC-C結合を可能にします.
- 伝統的に不活性なC-H債券の機能化のための戦略を確立する.
主な方法:
- 伝統的な非反応性C-Hボンドの指向的な割れ方
- 活性化されたC−H結合をすぐに利用可能なアルケーンと結合させる.
- 窒素-水素結合のリレー光還元誘導酸化によって達成されたアミド誘導選択性.
主要な成果:
- 活性化されていない sp3 C-H ボンドでC-C ボンドの形成を成功させる.
- 複数の区別がつかないC-H結合を持つ分子において高い選択性を示した.
- フォトレドックス触媒を用いたC−C結合構築の新たな経路を確立した.
結論:
- 開発された方法論は,C-HサイトでのC-C結合形成のための強力なツールを提供します.
- このアプローチは 複雑な分子構造にアクセスするための 合成化学者のツールキットを拡張します
- この発見は,特に水素原子移転を含むC-H機能化戦略に関するさらなる研究にインスピレーションを与えると期待されている.
関連する概念動画
Photochemical Electrocyclic Reactions: Stereochemistry
2.4K
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
2.4K
Thermal and Photochemical Electrocyclic Reactions: Overview
3.1K
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.
3.1K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.8K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.8K
Cycloaddition Reactions: MO Requirements for Thermal Activation
5.0K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
5.0K
Cycloaddition Reactions: Overview
3.7K
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.
3.7K
Thermal Electrocyclic Reactions: Stereochemistry
2.7K
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.
2.7K

![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
