光诱导的终端基因的选择性 perfluoroalkylation 通过电子捐赠者-接受者复合体
Xiaolin Shi1,2,3, Bo Yu1,2,3,4, Xin Zhou1,2,3
1CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China. yangyong@qibebt.ac.cn.
这项研究引入了一种新方法,用于使用光和醇离子选择性地 perfluoroalkylation 的alkynes. 这种方法可以有效地合成多种多基化化合物,为现有方法提供了有价值的替代方案.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 化学 的化学
背景情况:
- perfluoroalkylated 化合物在制药和材料科学中至关重要.
- 合成这些化合物的传统方法可能是苛刻或低效的.
- 开发新的,选择性的和温和的合成策略是必不可少的.
研究的目的:
- 开发一种光诱导方法,用于终端基因的选择性 perfluoroalkylation.
- 探索非共价相互作用在驱动反应中的作用.
- 合成一个多样化的 perfluoroalkylated 和的图书馆.
主要方法:
- 采用了一种光诱导反应,其中涉及甲基醇阳离子和甲基化物.
- 通过调节溶剂来精确控制反应条件.
- 进行了机制研究,以阐明反应途径,包括EDA复合体的形成.
主要成果:
- 实现了终端基因的选择性基化.
- 合成了37种结构多样化的 perfluoroalkylated 基和基.
- 获得的产品,包括药物中间制品,如伊布洛芬和empagliflozin,在高达92%的收益率.
结论:
- 开发的战略提供了一种高效和有选择性的合成高基化化合物的方法.
- 非共价相互作用和溶剂调是反应成功的关键.
- 这种方法补充了传统方法,并为有机合成提供了有价值的工具.
更多相关视频
09:54Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
06:49Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
相关概念视频
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.
Electrophilic Addition to Alkynes: Hydrohalogenation
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.
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.
Regioselectivity of Electrophilic Additions-Peroxide Effect
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.
