連続フローフォトレドックス触媒によるCO2によるスタイレンの直接β選択性炭酸酸化
Hyowon Seo1, Aofei Liu1, Timothy F Jamison1
1Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|September 28, 2017
まとめ
この研究では,温和な条件下で二酸化炭素 (CO2) を使用したスタイレンを直接ベータ選択的に水酸化する新しい方法が導入されています. フォトレドックス触媒のアプローチは,連続フローシステムで効率的に動作します.
科学分野:
- 有機化学
- カタリシス
- 持続可能な化学
背景:
- 炭酸を合成するには,炭酸酸化反応が不可欠である.
- CO2のような豊富な原料を用いた 選択的で効率的な方法の開発は 重要な課題です
- フォトレドックス触媒は新しい有機変異のための強力なプラットフォームを提供します.
研究 の 目的:
- ステロンの直接ベータ選択性炭化水素化を開発する.
- C1源として大気圧の二酸化炭素 (CO2) を利用する.
- フォトレドックス触媒による反応を連続流体システムで実施する.
主な方法:
- 炭化水素酸化反応のための光還元触媒を用いる.
- 効率とスケーラビリティを高めるために 連続フロー化学を使用します
- 様々な機能化されたスタイレンとの反応を調査する.
主要な成果:
- ステロンの直接ベータ選択性炭化水素酸化を達成した.
- CO2の大気圧をうまく使った
- 末端型,アルファ置換型,ベータ置換型スタイレンを含む広範な基板範囲が実証されています.
結論:
- 開発された方法は,ステレンとCO2からベータ代用カルボキシル酸への効率的な経路を提供します.
- 継続的な流れでのフォトレドックス触媒は,持続的なC−C結合形成のための実行可能な戦略です.
- この方法論は,有機合成におけるCO2の合成有用性を拡大します.
関連する概念動画
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 Benzene to Cyclohexane: Catalytic Hydrogenation
6.0K
Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...
6.0K
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
Regioselectivity and Stereochemistry of Hydroboration
9.5K
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 stereochemistry.
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 stereochemistry.
9.5K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.1K
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.
9.1K
Hydroboration-Oxidation of Alkenes
11.7K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
11.7K


