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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
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Clarifying Stereochemical Outcomes in Radical-Initiated Vinyl Cyclopropane Cycloadditions within the Beckwith-Houk

Caitlyn O Agee1, Het Vyas2, Brandon S Portela3

  • 1Department of Chemistry and Biochemistry, UNC Wilmington, Wilmington, NC, USA.

Organic Chemistry Frontiers : an International Journal of Organic Chemistry
|July 3, 2026
PubMed
Summary

This study reveals errors in previously assigned cyclopentane configurations from radical cycloaddition reactions. Combining Density Functional Theory (DFT) calculations with quantitative Nuclear Overhauser Effect (qNOE) NMR experiments provides a robust method for accurate stereochemical assignment.

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Published on: February 7, 2019

Area of Science:

  • Organic Synthesis
  • Stereochemistry
  • Computational Chemistry

Background:

  • The (3+2) cycloaddition reaction is crucial for synthesizing cyclopentane frameworks found in pharmaceuticals.
  • Catalytic radical cascade reactions are widely used, but stereochemical assignments can be inconsistent.
  • Previous studies may contain misassigned relative configurations of cyclopentane products.

Purpose of the Study:

  • To address discrepancies in the stereochemical assignment of cyclopentanes from radical (3+2) cycloadditions.
  • To develop and validate a reliable method for determining relative configurations in complex organic molecules.
  • To highlight the necessity of integrating computational and experimental techniques for accurate structural elucidation.

Main Methods:

  • Utilized Density Functional Theory (DFT) calculations to predict chemical shifts and coupling constants.
  • Employed 1D quantitative Nuclear Overhauser Effect (qNOE) NMR experiments for stereochemical analysis.
  • Integrated DFT predictions with experimental qNOE data for definitive configuration assignments.

Main Results:

  • Uncovered discrepancies in originally assigned trans configurations of cyclopentane products.
  • Demonstrated that DFT or NOESY data alone were insufficient for confident stereochemical assignment.
  • Established the combined approach of DFT and qNOE as a powerful tool for configurational verification.

Conclusions:

  • The integration of DFT calculations and experimental qNOE data is essential for accurate stereochemical assignment.
  • This methodology offers a general and robust approach applicable to various complex organic molecules.
  • Correct stereochemical assignment is critical for understanding the biological activity and pharmaceutical applications of cyclopentane derivatives.