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Photo-NHC Catalysis: Accessing Ketone Photochemistry with Carboxylic Acid Derivatives

Photo-NHC Catalysis: Accessing Ketone Photochemistry with Carboxylic Acid Derivatives

Photo-NHC Catalysis: Accessing Ketone Photochemistry with Carboxylic Acid Derivatives
Image Credit: Thieme

M. N. Hopkinson,* A. Mavroskoufis – 2020

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 while 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 where the NHC influences the absorption wavelength and inherent photochemical reactivity of the carbonyl group during the catalytic cycle.

Title
34. Photo-NHC Catalysis: Accessing Ketone Photochemistry with Carboxylic Acid Derivatives
Author
M. N. Hopkinson,* A. Mavroskoufis
Publisher
Synlett
Date
2020
Identifier
DOI: 10.1055/s-0040-1706472
Source(s)
Citation
Synlett, 2020, In Press, DOI: 10.1055/s-0040-1706472.
Type
Text