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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
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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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Stereoretentive radical cross-coupling.

Jiawei Sun1, Jiayan He1, Luca Massaro1

  • 1Department of Chemistry, Scripps Research, La Jolla, CA, USA.

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|April 22, 2025
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Summary
This summary is machine-generated.

This study introduces a novel method for enantioselective radical cross-coupling, overcoming challenges in stereochemical control. It enables stereospecific reactions using readily available materials and an inexpensive catalyst.

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Stereoselective Synthesis

Background:

  • Radical cross-coupling offers advantages for synthesizing complex molecules, particularly with saturated systems, due to mild conditions and high chemoselectivity.
  • However, achieving enantiospecific radical cross-coupling has been a significant challenge due to the rapid racemization of radical intermediates.
  • Previous approaches relied on bespoke chiral ligands or diastereoselective control, limiting broader applicability.

Purpose of the Study:

  • To develop a general and efficient method for enantiospecific radical cross-coupling.
  • To enable stereospecific and stereoretentive coupling of enantioenriched alkyl fragments with (hetero)aryl halides.
  • To overcome the inherent difficulty of controlling stereochemistry in radical reactions.

Main Methods:

  • Utilized readily accessible enantioenriched sulfonylhydrazides as radical precursors.
  • Employed low loadings of an inexpensive, achiral nickel catalyst.
  • Performed radical cross-coupling reactions between enantioenriched alkyl fragments and (hetero)aryl halides.
  • Conducted computational studies to elucidate reaction mechanisms.

Main Results:

  • Achieved the first examples of enantiospecific and stereoretentive radical cross-coupling.
  • Demonstrated the utility of sulfonylhydrazides and achiral nickel catalysis for this transformation.
  • Showcased the coupling of enantioenriched alkyl fragments with (hetero)aryl halides without chiral ligands or external redox agents.
  • Computational analysis revealed a unique nickel-bound diazene intermediate facilitating C-C bond formation via N2 extrusion.

Conclusions:

  • This work presents a breakthrough in enantioselective radical chemistry, providing a practical solution for stereospecific C-C bond formation.
  • The developed method broadens the scope of radical cross-coupling by enabling precise stereochemical control.
  • The findings pave the way for more efficient synthesis of complex chiral molecules using radical pathways.