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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

2.6K
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...
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Preparation of Alkynes: Alkylation Reaction02:27

Preparation of Alkynes: Alkylation Reaction

9.4K
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
9.4K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation02:47

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

19.8K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
19.8K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

6.9K
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.
6.9K
α-Alkylation of Ketones via Enolate Ions01:10

α-Alkylation of Ketones via Enolate Ions

2.4K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
2.4K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

1.4K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.4K

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Photo-Induced Cross-Linking of Unmodified Proteins PICUP Applied to Amyloidogenic Peptides
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ピ-アリルパラジウム複合体を用いたチロシン選択タンパク質アルキル化.

S David Tilley1, Matthew B Francis

  • 1Department of Chemistry, University of California, Berkeley, 94720-1460, USA.

Journal of the American Chemical Society
|January 26, 2006
PubMed
まとめ

研究者らは,タイロシン残基をターゲットにすることでタンパク質を改変する新しいパラジウム触媒反応を開発した. この方法は,水中のタンパク質の機能化を可能にし,合成リポタンパク質を作成し,新しいタンパク質修飾戦略を提供します.

科学分野:

  • 化学生物学 化学生物学とは
  • タンパク質化学 タンパク質化学
  • オーガニック・シンセシス オーガニック・シンセシス

背景:

  • タンパク質の改変は,生化学的研究と医薬品開発において極めて重要です.
  • 特定のアミノ酸残基をターゲットにすることで,タンパク質の機能化を正確に制御できます.
  • 既存の方法は,しばしば有機溶剤または厳しい条件を必要とし,その適用性を制限します.

研究 の 目的:

  • 新しい,選択的なタンパク質改変反応を開発する.
  • 室温で水溶液中のタンパク質の機能化を可能にします.
  • 合成リポタンパク質を作成し,新しいタンパク質改変戦略を探求する.

主な方法:

  • タイロシン残基のパラジウム触媒によるアリルアルキル化.
  • アルリルアセテートおよびカルバマート前駆体から生成された電子性PI-アルリル中間物の使用.
  • SDS-PAGEで検出するための光アルリルアセテートの合成.
  • タイロシン選択性を確認するためのトリプシン消化物の分析.
  • 溶解性の切り替えのための水溶解性グループ (タウリン由来カルバメート) の適用.

主要な成果:

さらに関連する動画

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Cell-Type Specific Protein Purification and Identification from Complex Tissues Using a Mutant Methionine tRNA Synthetase Mouse Line
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  • 室温の水溶液中のタンパク質 (キモトリプシノゲンA,MS2) の成功変異.
  • 反応のタイロシン選択性を実証した.
  • タンパク質に防水性ファルネシルとC17鎖を装着する.
  • C(17) アルキル化タンパク質は,脂質ベジクルと関連を示した.
  • 光ラベルとSDS-PAGEを使用して,改変されたタンパク質の検出を容易にした.
  • 結論:

    • タイロシン残基を標的とした,新しい多用途のタンパク質改変反応が確立されました.
    • この方法は,水中でのタンパク質機能化を可能にし,水害性鎖の設置も含む.
    • この技術は,合成リポタンパク質への便利な経路を提供し,タンパク質エンジニアリングの能力を拡張します.