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

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.

1 Introduction

2 Photo-NHC Catalysis

3 Conclusions

Key words

photochemistry - N-heterocyclic carbenes - organocatalysis - photoenolization - acid fluorides - annulation - cycloaddition - carbonyls

Publication History

Received: 18 August 2020

Accepted after revision: 27 August 2020

Article published online:
28 September 2020

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