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N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides
Author(s) -
Mavroskoufis Andreas,
Rajes Keerthana,
Golz Paul,
Agrawal Arush,
Ruß Vincent,
Götze Jan P.,
Hopkinson Matthew N.
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201914456
Subject(s) - carbene , chemistry , catalysis , reactivity (psychology) , ketone , photochemistry , diels–alder reaction , organocatalysis , stoichiometry , medicinal chemistry , organic chemistry , enantioselective synthesis , medicine , alternative medicine , pathology
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.