期刊
SYNLETT
卷 32, 期 2, 页码 95-101出版社
GEORG THIEME VERLAG KG
DOI: 10.1055/s-0040-1706472
关键词
photochemistry; N-heterocyclic carbenes; organocatalysis; photoenolization; acid fluorides; annulation; cycloaddition; carbonyls
资金
- Deutsche Forschungsgemeinschaft (DFG, German Research foundation) [420535461]
Excitation of carbonyl groups is a widely used activation mode in photochemistry, but many transformations are limited to aldehydes and ketones. This study introduces a novel strategy using N-heterocyclic carbene (NHC) organocatalyst to enable "ketone-like" photochemistry with carboxylic acid derivatives, demonstrating the feasibility of photoenolization/Diels-Alder reactions.
Excitation of carbonyl groups is one of the most widely employed activation modes in photochemistry. Many synthetically important transformations, however, are successful only with aldehydes and ketones; substrates at the carboxylic acid oxidation level remain underrepresented. We have developed a conceptually novel strategy for enabling 'ketone-like' photochemistry with carboxylic acid derivatives that employs an N-heterocyclic carbene (NHC) organocatalyst. Using this 'Photo-NHC' catalysis approach, a proof-of-concept photoenolization/Diels-Alder (PEDA) reaction between acid fluorides and trifluoroacetophenones was developed. Stoichiometric studies and TD-DFT calculations supported a mechanistic scenario in which the NHC influences the absorption wavelength and inherent photochemical reactivity of the carbonyl group during the catalytic cycle.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据