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Photochemical Electrocyclic Reactions: Stereochemistry01:26

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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
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Light-Induced Reactivity Switch at O2-Activating Bioinspired Copper(I) Complexes.

Donglin Diao1, Anna Baidiuk1, Leo Chaussy1

  • 1Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, 13013 Marseille, France.

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|May 31, 2024
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Summary
This summary is machine-generated.

Researchers developed a light-induced reactivity switch for copper-oxygen intermediates using bioinspired complexes. This breakthrough enables selective C-H functionalization, offering new pathways in copper-oxygen chemistry.

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Area of Science:

  • Bioinorganic Chemistry
  • Photochemistry
  • Organometallic Chemistry

Background:

  • Earth-abundant metal-oxygen intermediates possess high oxidation states, making their light-induced reactivity challenging to explore.
  • The photoinduced reactivity of copper-dioxygen (Cu-O2) intermediates is largely unexplored due to O2 photoejection under irradiation.

Purpose of the Study:

  • To investigate the light-induced reactivity switch of bioinspired O2-activating copper(I) complexes.
  • To demonstrate a novel method for selective C-H functionalization using photochemistry in Cu-O2 chemistry.

Main Methods:

  • Utilized bioinspired copper(I) complexes with tris(2-pyridyl-methyl)amine (TPA) ligands.
  • Investigated both open and caged copper(I) complexes with internal aryl ether substrates.
  • Employed photochemical irradiation and reactivity studies, supported by (TD-) DFT calculations.

Main Results:

  • Achieved a light-induced reactivity switch in Cu-O2 chemistry, a key precedent.
  • Demonstrated selective conversion of internal aryl ether to a phenolate-CH2- moiety with excellent yields under light.
  • Observed standard oxidative cleavage in the absence of light, contrasting with the photoinduced reaction.

Conclusions:

  • The study establishes a precedent for light-induced reactivity switching in Cu-O2 chemistry.
  • The developed method allows for selective C-H functionalization and easy postfunctionalization of TPA ligands.
  • A mechanism involving monomeric cupric-superoxide dependent reactivity, promoted by light, is proposed.