水素結合誘導光触媒水素化:電子制御を克服する
Mohammad B Khaled1, Roukaya K El Mokadem1, Jimmie D Weaver1
1Department of Chemistry, Oklahoma State University , Stillwater, Oklahoma 74078, United States.
Journal of the American Chemical Society
|August 25, 2017
まとめ
新しい水素結合戦略は,酸化アレンの光触媒C-F機能化における地域選択性を制御する. Januviaのような有価な化合物の効率的な合成を可能にします
科学分野:
- 有機化学
- 光触媒
- フッ素化学
背景:
- 光触媒C-F機能化により,多化アレンの合成が可能である.
- 地域選択性は通常,合成の範囲を制限する基板電子によって制御される.
- ラジカルアニオンからのフッ化物の断片化は,地域選択性を決定する.
研究 の 目的:
- C-F機能化の地域選択性に対する水素結合の影響を調査する.
- 分子内水素結合による水素化における速度の加速を調査する.
- 商業的に重要なフッ素化合物の製造における合成の有用性を実証する.
主な方法:
- 光触媒C-F機能化反応
- ラジカルアニオンの中間物質の調査
- 水素結合による地域選択性研究
- ジャヌビアの前駆体合成
主要な成果:
- 戦略的に配置された水素結合は,地域選択性の固有の電子制御を覆す.
- 水素結合に関与するC−F結合の水素化において顕著な速度加速が観察された.
- 水素結合はC−F結合の断片化とフッ化物の流出を促進する.
- Januviaの重要な中間物質の迅速な合成が達成されました.
結論:
- 水素結合は,C-F機能化における地域選択性を制御する強力なツールである.
- 開発された方法は,重要な多化アルネへのより効率的な経路を提供します.
- このアプローチは,医薬品の中間物質を合成するための新しい戦略を提供します.
関連する概念動画
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
2.3K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
2.3K
Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control
4.2K
The addition of a hydrogen halide to 1,3-butadiene gives a mixture of 1,2- and 1,4-adducts. Since more substituted alkenes are more stable, the 1,4-adduct is expected to be the major product. However, the product distribution is strongly influenced by temperature; low temperature favors the 1,2-adduct, whereas the 1,4-adduct is predominant at high temperature.
4.2K
Catalysis
31.0K
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.
31.0K
Reduction of Alkenes: Catalytic Hydrogenation
14.5K
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...
14.5K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.9K
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...
3.9K
Acid Halides to Carboxylic Acids: Hydrolysis
3.7K
Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...
3.7K


