ディエンとフォスフィン酸化物のエナンチオセレクティブカップリング
Shao-Zhen Nie1,2, Ryan T Davison1, Vy M Dong1
1Department of Chemistry , University of California , Irvine , California 92697 , United States.
Journal of the American Chemical Society
|November 20, 2018
まとめ
この研究は,単純なダイエンとフォスフィン酸化物からキラルアリルフォスフィン酸化物を生成するための新しいパラジウム触媒反応を導入する. この突破は 優れた制御を伴う 有価な有機リン化合物への 新たな経路を提供します
科学分野:
- 有機化学
- カタリシス
- オルガノフォスファース化学
背景:
- アリル酸ホスフィンは重要な合成中間物質である.
- キラルアリルフォスフィン酸化物を合成するための既存の方法は限られている.
- 非対称な触媒は,エナチオメリックに濃縮された化合物を生成するための強力なアプローチを提供します.
研究 の 目的:
- 1,3-ダイエンの新しいパラジウム触媒型分子間ヒドロフォスフィニレーションを開発する.
- キラルアリルフォスフィン酸化物の形成において高いエナンチオセレクティブ性と地域選択性を達成する.
- 有価な有機リン基を生産する新しい方法を確立する
主な方法:
- パラジウム触媒による結合反応
- 基質として商品の1,3-ダイエンを利用する.
- 空気に安定したフォスフィン酸化物を結合パートナーとして使用する.
主要な成果:
- キラル・アリル・フォスフィン・オキシドの合成に成功
- 反応において高いエナチオとレギオコントロールを示した.
- ダイエンの第1次非対称的水リン酸化を確立した.
結論:
- 開発されたPd触媒方式は,キラルアリルフォスフィン酸化物への効率的な経路を提供します.
- この方法論は,複雑な有機リン化合物を合成するためのツールキットを拡張します.
- 反応の高い選択性により,キラル構造ブロックの構築に価値があります.
さらに関連する動画
関連する概念動画
Oxidation Numbers
42.6K
In redox reactions, the transfer of electrons occurs between reacting species. Electron transfer is described by a hypothetical number called the oxidation number (or oxidation state). It represents the effective charge of an atom or element, which is assigned using a set of rules.
42.6K
Diels–Alder Reaction: Characteristics of Dienes
5.3K
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable,...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable,...
5.3K
Structure of Conjugated Dienes
7.4K
Introduction
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
7.4K
Stability of Conjugated Dienes
4.4K
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
4.4K
Pyruvate Oxidation
168.8K
After glycolysis, the charged pyruvate molecules enter the mitochondria via active transport and undergo three enzymatic reactions. These reactions ensure that pyruvate can enter the next metabolic pathway so that energy stored in the pyruvate molecules can be harnessed by the cells.
First, the enzyme pyruvate dehydrogenase removes the carboxyl group from pyruvate and releases it as carbon dioxide. The stripped molecule is then oxidized and releases electrons, which are then picked up by NAD+...
First, the enzyme pyruvate dehydrogenase removes the carboxyl group from pyruvate and releases it as carbon dioxide. The stripped molecule is then oxidized and releases electrons, which are then picked up by NAD+...
168.8K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
1.7K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.7K


