Density Functional Theory Determination of an Axial Gateway to Explain the Rate and Endo Selectivity Enhancement of Diels-Alder Reactions by Bis(oxazoline)-Cu(II)

Jason DeChancie, Orlando Acevedo, Jeffrey D. Evanseck

Research output: Contribution to journalArticle

25 Scopus citations

Abstract

A novel conceptual model and unique understanding of rate and endo selectivity enhancements delivered by bis(oxazoline)-Cu(II) Lewis acid catalysts in the Diels-Alder reaction of cyclopentadiene and acrylate imide is presented. Despite previously reported kinetic and spectroscopic studies, the physical reasons for endo selectivity and rate enhancements remain poorly understood. Large-scale density functional calculations using Becke three-parameter density functional theory with the nonlocal correlation of Lee, Yang, and Parr and the 6-31G(d) basis set have been carried out for the first time to understand the geometric and energetic consequences of C 2-substituent variation. The unique positioning of the tert-butyl C2-substituent with respect to the diene, referred to as the "axial gateway", maintains the electrophilicity of the catalyst by shielding the reactive metal center from nucleophilic attack. The interplay between steric and electronic factors is crucial to understanding the observed enhanced rates and endo selectivity.

Original languageEnglish (US)
Pages (from-to)6043-6047
Number of pages5
JournalJournal of the American Chemical Society
Volume126
Issue number19
DOIs
StatePublished - May 19 2004
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Density Functional Theory Determination of an Axial Gateway to Explain the Rate and Endo Selectivity Enhancement of Diels-Alder Reactions by Bis(oxazoline)-Cu(II)'. Together they form a unique fingerprint.

  • Cite this