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

Lookup NU author(s): Dr Matt HopkinsonORCiD

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Abstract

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.

Publication metadata

Author(s): Hopkinson MN, Mavroskoufis A

Publication type: Review

Publication status: Published

Journal: Synlett

Year: 2021

Volume: 32

Issue: 02

Pages: 95-101

Print publication date: 15/01/2021

Online publication date: 28/09/2020

Acceptance date: 27/08/2020

ISSN (print): 0936-5214

ISSN (electronic): 1437-2096

URL: https://doi.org/10.1055/s-0040-1706472

DOI: 10.1055/s-0040-1706472

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