ストレントアルキンが,銅との複合化によるクリック反応から一時的に保護される
Suguru Yoshida1, Yasutomo Hatakeyama, Kohei Johmoto
1Laboratory of Chemical Bioscience, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University , 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan.
Journal of the American Chemical Society
|September 19, 2014
まとめ
銅の塩を使用したサイクロオクチンの一時的な保護は,選択的なクリック化学を可能にします. この方法により,特定のアルキンの部位で制御された結合が可能になり,サイクロオクチンの誘導体は様々な用途でより容易に入手できます.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 化学生物学 化学生物学とは
背景:
- クリック化学,特に銅で触媒化されたアジド-アルキンサイクロアディション (CuAAC) は,分子構築のための強力なツールです.
- サイクロオクチンは多用途な構成要素ですが,望ましくない反応を受け,その有用性を制限することがあります.
研究 の 目的:
- 早期の反応を防ぐために,サイクルオクトインの一時的な保護戦略を開発する.
- 他の反応性グループの存在において,サイクロオクトインの選択的機能化を可能にする.
主な方法:
- サイクロオクチンとカチオンの銅 (((I) 塩を複合して1:1複合体を形成し,アルキンを一時的に遮断する.
- 末端アルキンの部分を持つサイクロオクトインに対する保護方法の適用.
- 選択的銅触媒クリック結合は,保護されていない端末アルキンでアジドと結合する.
主要な成果:
- 銅 ((I) 複合は,シクロオクチンがアジドと反応するのを効果的に防ぐことができた.
- 選択的結合は,保護された内部アルキンの存在下で,端末アルキンで達成されました.
- この戦略は,複雑なサイクロオクチンの誘導体の合成を容易にした.
結論:
- サイクルオクトインの新型一時的な保護方法は,銅 (I) 塩を用いて確立されています.
- この方法は,クリック化学で正交的な制御を提供し,機能化されたサイクロオクトインのアクセシビリティを強化します.
さらに関連する動画
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
関連する概念動画
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
6.8K
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.
6.8K
02:27Preparation of Alkynes: Alkylation Reaction
9.1K
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.
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.
9.1K
02:38Electrophilic Addition to Alkynes: Halogenation
7.3K
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
7.3K
02:35Electrophilic Addition to Alkynes: Hydrohalogenation
9.3K
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
9.3K
02:40Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
8.8K
Introduction
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
8.8K
02:34Preparation of Alkynes: Dehydrohalogenation
16.9K
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
16.9K