COMPUTATIONAL MODELING OF SEMIBULLVALENE SYNTHESIS

CHEM260 FALL 2016

KEYANG SUN

Semibullvalene is a synthetically fascinating fluxional molecule that undergoes

rapid cope rearrangement even at -110oC [3] and has prompted countless studies
exploring its synthesis. While the principle pathways to semibullvalene all include
isomerization of cyclic precursors such as barrelene, cyclooctatetraene and
tricyclo[3.3.0.02.8]octa-3,7-diene [1], Sauer et. al. proposed an alternative approach to
semibullvalene synthesis using 3,3’-bicyclopropenyl and 1,2,4,5-tetrazinediester in a
sequence of cycloaddition-cycloelimination steps accompanied by dinitrogen extrusion
[2]; the mechanism can also introduce structural variations by substitution of 1,2,4,5-
tetrazinediester.

In the efforts of Sauer et. al. to elucidate the reaction mechanism and intermediate
structures, over 30 chemicals were synthesized and characterized [2]. As experiments are
often taxing, computational studies can be done on a proposed mechanism to examine the
accessibility of a synthetic route based on its energetics. Intermediate energies can be
obtained to assess the thermodynamics of the reaction, while transition state energies can
explicate the kinetics of a reaction mechanism [1]. This computational study aims to
supplement the experimental research by computing a free energy reaction coordinate
diagram of the mechanism presented by Sauer et. al., examine the molecular orbital
interactions, and compare the thermodynamics of this new approach to afford
semibullvalene with the established isomerizations reactions.

I will perform Monte Carlo conformation searches on the reactants, intermediates

and semibullvalene product in the mechanistic scheme provided by Sauer et. al. and of
the four aforementioned cyclic precursors in Maestro [4]; QM optimizations will be done
on the resultant structures at the B3LYP/6-31G** level of theory in Q-Chem,
supplemented by frequency calculations [4]. With this information, it is possible to assess
the specific steps that influence the reversibility and the thermal character of the overall
reaction. The reaction pathway between intermediates will be interpolated using the
freezing string method followed by transition state searches that would locate the
energetic saddle points along the reaction coordinate [5]. This method can also be used to
elucidate the cope rearrangement energy barrier between the degenerate semibullvalene
tautomers as well as the kinetic feasibility of the reaction; It is possible to generate a
rigorous rate expression from these ab initio calculations. In addition, molecular orbital
plots can be generated using the basis sets to visualize the orbital interactions in the
electrocyclization steps of the mechanism [1].

[1] Semibullvalene. Chem 260 Suggested Project: Semibullvalene.

https://docs.google.com/ document/u/1/d/1Tzlcdnr-
dOqAOhSEHa7g9gKjTXAEfm6qreKOMEk9FYQ/pub (accessed Oct. 15, 2016)
[2] Sauer, J. et. al. “An one-pot synthesis of semibullvalenes and its mechanism.” Eur. J.
Org. Chem., 2002, 791-801.
[3] Zhang, S. et. al. ”Semibullvalene and Diazasemibullvalene: Recent Advances in the
Synthesis, Reaction Chemistry, and Synthetic Applications.” Acc. Chem. Res., 2015, 48
(7), 1823–1831.
[4] Computational Methods Summary. MCGF – College of Chemistry, University of
California, Berkeley. https://docs.google.com/document/u/1/d/1w68nqqqr-
OYZXv97yXHbA_xAfj2ZTMQY_bE5YRy5AZk/pub (accessed Oct. 15, 2016).
[5] Q-Chem 4.3 User’s Manual. http://www.q-chem.com/qchem-website/manual_4-
1.html (accessed Oct. 15, 2016).