アリルメチル硫化物は,ロジウム触媒によるアルキンカルボチオレーションの基質として用いられる:活性化群のリサイクルによるアレン機能化
Joel F Hooper1, Adrian B Chaplin, Carlos González-Rodríguez
1Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, UK.
Journal of the American Chemical Society
|February 3, 2012
まとめ
この研究では,アリルメチル硫化物とアルキンを用いて,アレンをロジウム触媒化カルボチオライゼーションに導入しています. この方法により,アルケニル硫化物が効率的に生成され,炭水化物とヘテロサイクルの合成に役立ちます.
科学分野:
- 有機化学 オーガニック・ケミストリー
- カタリシス カタリシス カタリシス
- 合成方法論 合成方法論
背景:
- アリルメチル硫化物は,一般的な有機化合物である.
- アレンの効率的な機能化は,有機合成において極めて重要です.
- C-S結合形成のための新しい触媒方法の開発は,活発な研究分野です.
研究 の 目的:
- アレンの機能化のための新しいロジウム ((I) -触媒化された方法を開発する.
- アレンの末端アルキンによるカルボチオライゼーションを達成するために.
- 合成されたアルケニル硫化物によるさらなる合成変換の有用性を調査する.
主な方法:
- アリルメチル硫化物と末端アルキンの間のロジウム ((I) 触媒反応.
- 水酸化を含む三要素カスケード反応.
- 反応経路を解明するためのメカニズム研究.
主要な成果:
- アルケニル硫化物のカルボチオレーションによる効率的な合成.
- カスケード配列における水酸化と成功した組み合わせ.
- 炭水化物とヘテロサイクルの形成における製品の実証された有用性.
- 触媒サイクルに関する機械学的洞察を提供した.
結論:
- アレンの新しいRh (I) -触媒化されたカルボチオライゼーションが確立されました.
- 開発された方法は,機能化されたアルケニル硫化物への効率的な経路を提供します.
- これらの製品は,循環性化合物を構築するための貴重な中間物質として機能します.
関連する概念動画
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Preparation of Alkynes: Alkylation Reaction
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.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
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.
Preparation of Alkynes: Dehydrohalogenation
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.

