基于FeIII的Eutectic混合物作为多功能和可重复使用的反应介质,用于有效和选择性地将基转化为碳化合物
Marina Ramos-Martín1, Nicolas Ríos-Lombardía1,2, Javier González-Sabín2
1Laboratorio de Química Sintética Sostenible (QuimSinSos), Departamento de Química Orgánica e Inorgánica, (IUQOEM), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Química, Universidad de Oviedo, E33071, Oviedo, Spain).
Chemistry (Weinheim an der Bergstrasse, Germany)
|July 13, 2023
概括
在温和的条件下,一种新的以铁为基础的深溶解剂 (DES) 有效地催化了基因的化到甲基基和氧化到1,2-二基. 这种可持续的系统可以轻松隔离产品和催化剂回收利用,避免有毒金属和VOC溶剂.
科学领域:
- 绿色化学 绿色化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 开发可持续和高效的催化系统对于现代有机合成至关重要.
- 基因功能化的传统方法通常依赖于昂贵的贵金属和恶劣的条件.
- 铁基催化剂提供了更便宜,更丰富的替代品,但它们在选择性基因转换中的应用仍然是研究的活跃领域.
研究的目的:
- 开发一种简单,高效和可持续的协议,用于选择性化终端基因到甲基基.
- 探索一种以铁为基础的深溶剂 (DES) 作为促进剂和溶剂对基转换的实用性.
- 为了研究这个系统在氧化内部基因到1,2-二基的潜力.
主要方法:
- 使用一种易于合成和廉价的铁 (III) 化物/甘油 (FeCl3·6H2O/Gly, 3:1) 深度环氧混合物.
- 在温和的条件下 (45°C,空气) 进行了基水化反应,没有配体,共催化剂或有毒贵金属.
- 通过简单的和催化剂可回收性来研究产品分离.
- 使用相同的FeIII-DES系统探索内部基的氧化.
主要成果:
- 在30分钟内实现了终端基因到甲基基的选择性水合.
- 通过分离FeIII-DES来证明固体甲基的直接分离,消除了对挥发性有机化合物 (VOC) 溶剂的需求.
- 成功地回收了FeIII-DES催化剂多达八次用于水化反应.
- 展示了内部基因到1,2-二基的高效氧化,可回收率高达三倍.
- 初步的机理学研究表明,甲基基和α-基是氧化途径中的中间体.
结论:
- 开发的FeIII-DES系统提供了一种绿色,具有成本效益和高效的基因功能化方法.
- 该协议的简单性,温和条件和可回收性使其成为传统方法的有吸引力的替代方案.
- 这项工作突出了DES作为有机合成中可持续反应介质和催化剂的潜力.
相关概念视频
02:27Preparation of Alkynes: Alkylation Reaction
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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.
10.3K
02:43E1 Reaction: Stereochemistry and Regiochemistry
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One of the critical aspects of the E1 reaction mechanism, as also observed in E2, is the regiochemistry, with multiple regioisomers obtained as products. In the example discussed, the presence of water as a weak base favors elimination over substitution to generate two alkenes. Given that alkenes’ stability increases with the number of alkyl groups across the double bond, typically, E1 reactions lead to the Zaitsev product, for this is more substituted and stable than the Hofmann product.
9.7K
02:34Preparation of Alkynes: Dehydrohalogenation
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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.
16.0K
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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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.
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02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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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.
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02:42Acidity of 1-Alkynes
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The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
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