シングル・アトミック・サイト・カタリストの電子的金属支柱相互作用による高地域選択性の創造
Wen-Hao Li1, Jiarui Yang1, Hongyu Jing1
1Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Journal of the American Chemical Society
|September 10, 2021
まとめ
研究者は,有機反応の地域選択性を正確に制御する新しい単原子位触媒 (Cu1-TiC) を開発した. この触媒は,枝分かれイソマーを避け,非常に線形なE型アルキン変換のための電子金属サポート相互作用 (EMSI) を強化します.
科学分野:
- カタリシス
- 有機化学
- 材料科学
背景:
- リガンドは,有機合成における地域選択性を制御するために伝統的に使用されている.
- 有機合成を進めるためには,新しい地域選択的制御方法の開発が不可欠です.
研究 の 目的:
- 強化された地域選択制御のための単原子サイト触媒 (SAC) の設計と合成.
- 反応選択性を調節する電子金属支柱相互作用 (EMSI) の役割を調査する.
主な方法:
- EMSI効果を活用した 単一原子位触媒Cu1-TiCを設計・合成した
- 触媒の性能を理解するために反応機構を研究した.
- π雲のバックドネーションを高めるために,一時的な電子豊富な特性を利用した.
主要な成果:
- 電子的に偏らないアルキンの高度な線形E型地域選択変換 (線形:分岐比>100:1) を達成した.
- 枝分かれした同位体形成を完全に回避した.
- 売上高 (トン数) が612台に達し,以前よりも3倍高い.
- SACの合成メカニズムにおける各要素の重要な役割を示した.
結論:
- 強いEMSIを持つ単原子位触媒 (SAC) は,均質な触媒における地域選択性を効果的に調節することができる.
- EMSIは以前は触媒の効率と耐久性を高めると知られていましたが,反応の選択性を制御する大きな可能性を示しています.
- 設計されたCu1-TiC触媒は,地域選択的な有機合成のための新しいパラダイムを提供します.
関連する概念動画
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.5K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.5K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
15.0K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
15.0K
Regioselectivity and Stereochemistry of Hydroboration
8.6K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.6K
Reduction of Alkenes: Catalytic Hydrogenation
12.8K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
12.8K
Catalysis
28.2K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
28.2K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.3K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
8.3K


