基酸与基因的银和基激活的SOMOphilic基化
Wenqian Du1, Rongjie Yang1, Jinhong Bai2
1School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China.
这项研究引入了一种有效的方法,通过将基与基酸结合起来,创建C(sp) -C(sp3) 键. 这种新型的交叉合反应为合成重要的有机分子提供了一种多功能方法.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 含基的分子是有机合成,药物发现和材料科学中至关重要的构建块.
- 构建碳-碳键的高效方法,特别是C ((sp) -C ((sp3) 链接,是非常受欢迎的.
研究的目的:
- 开发一种高效的协议,用于与各种基酸交叉合甲基因的C(sp) -C(sp3).
- 建立一种通用的合成策略,以获得含有基尼尔的化合物与多种基替代物的基替代物.
主要方法:
- 这项研究使用了bromoalkynes和初级,二级和三级基酸之间的白银和基介导的交叉合反应.
- 进行了机理学研究以阐明反应途径.
主要成果:
- 成功开发了一个有效的C(sp) -C(sp3) 交叉合协议.
- 反应通过一种涉及基生成,α-添加和β-消除的拟议机制进行.
- 该方法证明了广泛的基质范围,容纳了各种各样的基酸和甲基因.
结论:
- 报告中的交叉合策略提供了一种有价值的新方法,用于合成C{\displaystyle C} -C{\displaystyle C} -sp3的债券.
- 反应使用易于获得的起始材料,并在温和,易于管理的条件下运行.
- 这种方法为有机合成和药物发现中的应用提供了巨大的潜力.
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相关概念视频
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.
Acidity of 1-Alkynes
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.
Radical Substitution: Allylic Bromination
Base-Promoted α-Halogenation of Aldehydes and Ketones
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.
Halogenation of Alkenes
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
