通过西兰介导的基化激活脱水氨酸衍生物的Giese型化
Perry van der Heide1,2, Michele Retini3, Fabiola Fanini3
1Department of Chemical and Geological Sciences, University of Cagliari, S.S. 554, bivio per Sestu, 09042 Monserrato (CA), Italy.
研究人员使用光化学开发了一种新的无金属方法,用于用光化学方法对脱氨酸 (Dha) 衍生物的后期功能化. 这种方法可以轻微化,为生物结合物治疗和药物发现提供了潜力.
科学领域:
- 有机化学 有机化学
- 药用化学 医学化学
- 生物结合科学 生物结合科学
背景情况:
- 生物结合剂疗法越来越重要,推动对高效基架修改的需求.
- 后期阶段功能化 (LSF) 允许在合成结束时修改复杂分子.
- 脱氨酸 (Dha) 衍生物是有价值的LSF基质,因为它们具有反应性烯酸部分.
研究的目的:
- 提出一种新的,不含金属的光化学策略,用于脱氨衍生物的化.
- 建立一种温和而简单的方法,在基架上形成新的碳-碳键.
- 探索这种反应在水性介质中的潜力,以及功能化后的应用.
主要方法:
- 利用光诱导的西兰介导原子转移 (XAT) 来从有机化物生成基.
- 在光化学生成的基基和Dha衍生物之间采用Giese型反应.
- 通过使用衍生物作为光催化剂和三三甲基 (TTMS) 作为原子供体进行反应.
主要成果:
- 成功实现了Dha衍生物的无金属光化学化.
- 通过Giese类型的添加证明了新的C(sp3) -C(sp3) 债券的形成.
- 展示了反应与酸盐缓冲盐水 (PBS) 溶液的兼容性,表明了生物应用的潜力.
结论:
- 开发的方法为的后期功能化提供了一种温和而高效的途径.
- 这种光化学方法避免了对过渡金属的需求,简化了净化和扩大了适用性.
- 该战略对合成复杂的基于的生物结合物和候选药物具有前景.
更多相关视频
08:12A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
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
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.
Preparation of Alkynes: Dehydrohalogenation
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.
α-Alkylation of Ketones via Enolate Ions
Base-Promoted α-Halogenation of Aldehydes and Ketones
Radical Substitution: Allylic Bromination
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic...
