Mavroskoufis Andreas, Rajes Keerthana, Golz Paul, Agrawal Arush, Ruß Vincent, Götze Jan P, Hopkinson Matthew N
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Takustraße 3, 14195, Berlin, Germany.
Angew Chem Int Ed Engl. 2020 Feb 17;59(8):3190-3194. doi: 10.1002/anie.201914456. Epub 2020 Jan 9.
The combination of light activation and N-heterocyclic carbene (NHC) organocatalysis has enabled the use of acid fluorides as substrates in a UVA-light-mediated photochemical transformation previously observed only with aromatic aldehydes and ketones. Stoichiometric studies and TD-DFT calculations support a mechanism involving the photoactivation of an ortho-toluoyl azolium intermediate, which exhibits "ketone-like" photochemical reactivity under UVA irradiation. Using this photo-NHC catalysis approach, a novel photoenolization/Diels-Alder (PEDA) process was developed that leads to diverse isochroman-1-one derivatives.
光活化与N-杂环卡宾（NHC）有机催化的结合，使得酰氟能够作为底物用于一种UVA光介导的光化学转化反应中，而这种反应此前仅在芳香醛和酮中观察到。化学计量学研究和TD-DFT计算支持了一种涉及邻甲苯酰基唑鎓中间体光活化的机理，该中间体在UVA照射下表现出“酮样”光化学反应性。利用这种光-NHC催化方法，开发了一种新型的光烯醇化/狄尔斯-阿尔德（PEDA）反应过程，该过程可生成多种异苯并二氢吡喃-1-酮衍生物。
