来自alkoxyaroylsilanes的光诱导的酒精和子生成:对竞争激进路径的机械洞察力
Yang Cheng1, Shu-Lin Zhang1, Jessika Lammert2
1Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, Shaanxi Provincial Key Laboratory of New Concept Sensors and Molecular Materials, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.
基二醇烯基 (BDIPS) 光性保护组为酒精保护提供了两个不同的途径. 反应结果取决于基质.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 有机合成 有机合成
背景情况:
- 乙基具有独特的光化学反应性,包括原子转移 (HAT) 和转移.
- 甲二醇 (BDIPS) 是一种新型的可照性保护组 (PPG),用于酒精.
- 用BDIPS保护的酒精表现出不同的光反应:甲醇中的脱保护和乙二中的重组.
研究的目的:
- 调查BDIPS-光反应中的机制差异.
- 阐明导致酒精释放或子形成的竞争性途径.
- 了解阿基西兰PPG的结构-活性关系.
主要方法:
- 五秒秒短暂吸收光谱学.
- 密度函数理论 (DFT) 的计算.
- 对模型化合物的系统研究 (1a,1b,1c) 和依赖溶剂的研究.
主要成果:
- 一个α-的存在有利于HAT通路,产生重新排列的子.
- 缺少α-能促进了silyl转移,从而实现了高效的酒精光保护.
- 溶剂 (甲醇与乙二) 影响BDIPS-乙烯的光反应结果.
结论:
- 当地的化学环境和基质结构决定了BDIPS-以太的光反应路径.
- 关于乙 PPG 的结构反应性的基本见解.
- 为设计可编程光响应系统提供了基础.
更多相关视频
14:22Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
Published on: April 15, 2013
06:31Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators
Published on: November 27, 2015
相关概念视频
Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
α-Alkylation of Ketones via Enolate Ions
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
Preparation of Alcohols via Addition Reactions
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...
