Display options
Cite
Heggen B, Patil M, Thiel W. Cyclization of an α,β-unsaturated hydrazone catalyzed by a BINOL-phosphoric acid: Pericyclic or not?. J Comput Chem. 2015;37(2):280-5doi: 10.1002/jcc.24044.
Heggen, B., Patil, M., & Thiel, W. (2016). Cyclization of an α,β-unsaturated hydrazone catalyzed by a BINOL-phosphoric acid: Pericyclic or not?. Journal of computational chemistry, 37(2), 280-5. https://doi.org/10.1002/jcc.24044
Heggen, Berit, et al. "Cyclization of an α,β-unsaturated hydrazone catalyzed by a BINOL-phosphoric acid: Pericyclic or not?." Journal of computational chemistry vol. 37,2 (2016): 280-5. doi: https://doi.org/10.1002/jcc.24044
Heggen B, Patil M, Thiel W. Cyclization of an α,β-unsaturated hydrazone catalyzed by a BINOL-phosphoric acid: Pericyclic or not?. J Comput Chem. 2016 Jan 15;37(2):280-5. doi: 10.1002/jcc.24044. Epub 2015 Sep 16. PMID: 26373256.
Copy Download .nbib Format: NLM
Share it on

J Comput Chem. 2016 Jan 15;37(2):280-5. doi: 10.1002/jcc.24044. Epub 2015 Sep 16.

Cyclization of an α,β-unsaturated hydrazone catalyzed by a BINOL-phosphoric acid: Pericyclic or not?.

Journal of computational chemistry

Berit Heggen, Mahendra Patil, Walter Thiel

Affiliations

  1. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.
  2. Centre for Excellence in Basic Sciences Health Centre, University of Mumbai, Vidhyanagaria Campus, Mumbai, 400098, India.

PMID: 26373256 DOI: 10.1002/jcc.24044

Abstract

Density functional theory is used to study the mechanism of the title reaction, one of the first catalytic asymmetric 6π-electrocyclizations observed experimentally. The benzylideneacetone-derived phenyl hydrazone is chosen as model substrate for the cyclization reaction, both in the protonated (A) and unprotonated (B) form, while the isoelectronic carbon analogue, 1,5-diphenylpentadienyl anion (C), serves as a reference for comparisons. The barrier to cyclization is computed to be more than 15 kcal/mol lower in A compared with B, in line with the observed acid catalysis. The relevant transition states to cyclization are characterized for A and C using orbital inspection, natural bond orbital analysis, nucleus independent chemical shifts, and stereochemical indicators. The cyclization of C is confirmed to be pericyclic, while that of A can be described as pseudopericyclic ring closure involving an intramolecular nucleophilic addition.

© 2015 Wiley Periodicals, Inc.

Keywords: density functional theory; electrocyclization; nucleus independent chemical shift; pseudopericyclic; transition state

Publication Types