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Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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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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Polar-Radical Cyclization Cascades with Magnesiated Nitriles.

Stephen Bolgunas1, Ehecatl Paleo2, Embarek Alwedi1

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Organic Letters
|May 4, 2023
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Naphthalene mediates a novel polar-radical addition-cyclization cascade, transforming magnesiated nitriles into diverse bicyclic ketones. This method efficiently creates complex cyclobutanones with multiple chiral centers in a single step.

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry
  • Reaction Mechanisms

Background:

  • Magnesiated nitriles are versatile synthons in organic chemistry.
  • Radical cyclization reactions are key for forming cyclic structures.
  • Developing efficient methods for synthesizing complex polycyclic ketones remains a challenge.

Purpose of the Study:

  • To develop a novel synthetic route to bi- and tricyclic ketones.
  • To explore the utility of a polar-radical addition-cyclization cascade.
  • To investigate the combination of this cascade with carbonyl-conjugate addition for complex molecule synthesis.

Main Methods:

  • Utilizing naphthalene as a single-electron oxidant.
  • Employing magnesiated ω-alkenylnitriles as substrates.
  • Performing a polar-radical addition-cyclization cascade followed by hydrolysis.
  • Integrating a 1,2:1,4-carbonyl-conjugate addition with the cascade.

Main Results:

  • Naphthalene effectively initiates a polar-radical cascade with magnesiated nitriles.
  • The reaction generates diverse bicyclo[3.2.0]heptan-6-ones through a nitrile-stabilized radical pathway.
  • Combining the cascade with conjugate addition yields complex cyclobutanones with four new C-C bonds and four chiral centers.
  • The synthetic operation offers a streamlined approach to intricate molecular architectures.

Conclusions:

  • The described polar-radical addition-cyclization cascade provides an efficient method for synthesizing bicyclic ketones.
  • This strategy enables the rapid construction of complex cyclobutanones with high stereochemical control.
  • The methodology holds significant potential for the synthesis of complex organic molecules and natural products.