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Range-Separated DFT Functionals are Necessary to Model Thio-Michael Additions.

Jennifer M Smith1, Yasaman Jami Alahmadi1, Christopher N Rowley1

  • 1Department of Chemistry, Memorial University of Newfoundland , St. John's, Newfoundland A1B 3X7, Canada.

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|November 20, 2015
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Summary
This summary is machine-generated.

Popular density functional theory (DFT) methods incorrectly model Michael-type additions. Range-separated DFT functionals accurately predict carbanion intermediates, crucial for understanding biochemical reactions involving thiols and alkenes.

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Area of Science:

  • Computational Chemistry
  • Organic Chemistry
  • Biochemistry

Background:

  • The Michael-type addition is a key reaction mechanism involving thiols and alkenes.
  • Previous computational models failed to identify carbanion intermediates, suggesting alternative reaction pathways.
  • This discrepancy arises from errors in common density functional theory (DFT) functionals.

Purpose of the Study:

  • To investigate the accuracy of DFT functionals in modeling Michael-type additions.
  • To identify computational methods that correctly predict carbanion intermediate stability.
  • To enable accurate modeling of biochemical reactions involving thiol-ene additions.

Main Methods:

  • Evaluation of various pure and hybrid DFT functionals (e.g., PBE, B3LYP).
  • Utilizing range-separated DFT functionals, specifically ωB97X-D.
  • Comparison of DFT results with high-level coupled cluster calculations (CCSD(T)).

Main Results:

  • Popular DFT functionals (PBE, B3LYP) erroneously predict no carbanion intermediate due to delocalization error.
  • These functionals favor spurious noncovalent charge-transfer complexes.
  • Range-separated DFT functionals, particularly ωB97X-D, accurately predict stable carbanion structures and energies.
  • ωB97X-D results show excellent agreement with CCSD(T) data.

Conclusions:

  • Range-separated DFT functionals resolve the inaccuracies of standard DFT methods for Michael-type additions.
  • Accurate computational modeling of thio-carbanion intermediates is now feasible.
  • This advancement facilitates the study of biochemical processes like drug modification of cysteine residues.