没有金属的基因的电性玻利性循环
Jaime Mateos-Gil1, Marcos Humanes1, Manuel A Fernández-Rodríguez1
1Departamento de Química Orgánica y Química Inorgánica, Instituto de Investigación Química "Andrés M. del Río", Universidad de Alcalá (IRYCIS), Alcalá de Henares, Madrid, Spain.
无金属玻利化循环提供了一条通往含循环化合物的多功能途径. 最近使用 Lewis 酸的进展使得在温和条件下能够有效地形成 C-B 和 C-C 键.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 有机化学 有机化学
背景情况:
- 无金属玻利化循环是合成含循环框架的关键.
- 这些反应利用易斯酸对基因的电友激活.
- 早期的方法具有有限的合成实用性,但最近的发展扩大了它们的范围.
研究的目的:
- 审查最近的进步,在不含金属的基的化循环.
- 突出这些反应的扩大范围和实际相关性.
- 确定增加分子多样性的未来机会.
主要方法:
- 使用 Lewis 酸 (例如 ClBcat, BCl3) 电友性激活基.
- 内分子核友性攻击以形成C-B和C-C或C-X键.
- 使用广泛的异构原子和碳基核友.
主要成果:
- 有效地构建多种化异质环和碳循环.
- 同时形成C-B和C-C或C-X债券.
- 产品通常被分离为多用途的酸.
- 温和的,没有过渡金属的反应条件.
结论:
- 无金属玻利化循环是一种强大的策略,用于合成含的异循环和碳循环.
- 最近的发展显著提高了这些反应的范围和效用.
- 合理的基质设计有望在未来扩大分子多样性.
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相关概念视频
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
Electrophilic Addition to Alkynes: Halogenation
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.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
Preparation of Alkynes: Alkylation Reaction
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.
Hydroboration-Oxidation of Alkenes
Electrophilic Addition to Alkynes: Hydrohalogenation
