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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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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
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Reactivity and selectivity modulation within a molecular assembly: recent examples from photochemistry.

Yeshua Sempere1, Martin Morgenstern1, Thorsten Bach2

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Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology
|December 16, 2021
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Photochemical reactions offer powerful synthetic routes but often lack selectivity. Molecular assemblies driven by non-covalent interactions enhance stereo- and chemoselectivity in these organic transformations.

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Area of Science:

  • Organic Chemistry
  • Photochemistry
  • Supramolecular Chemistry

Background:

  • Photochemical reactions are valuable tools in organic synthesis.
  • Controlling selectivity (stereo- and chemoselectivity) remains a challenge.
  • Molecular assemblies offer a strategy to improve selectivity.

Purpose of the Study:

  • To review recent examples of photochemical reactions.
  • To highlight how molecular assemblies dictate reaction outcomes.
  • To showcase selectivity control via non-covalent interactions.

Main Methods:

  • Formation of molecular assemblies between photosubstrates and host molecules.
  • Utilizing non-covalent weak interactions to drive assembly.
  • Analysis of photochemical reaction outcomes.

Main Results:

  • Demonstrated unique outcomes in photochemical reactions.
  • Showcased improved stereo- and chemoselectivity.
  • Highlighted the role of host-guest complexation.

Conclusions:

  • Molecular assemblies are key to controlling photochemical reactions.
  • Non-covalent interactions are crucial for achieving selectivity.
  • This approach expands the scope of synthetic photochemistry.