An ab initio study on the allene-isocyanic acid and ketene-vinylimine [2 + 2] cycloaddition reaction paths

The Journal of Physical Chemistry. a
Joanna E Rode, Jan Cz Dobrowolski

Abstract

The reaction paths of [2 + 2] cycloadditions of allene (H2C=C=CH2) to isocyanic acid (HN=C=O) and ketene (H2C=C=O) to vinylimine (H2C=C=NH), leading to all the possible 14 four-membered ring molecules, were investigated by the MP2/aug-cc-pVDZ method. In the two considered reactions, the 2-azetidinone (beta-lactam) ring compounds were predicted to be the most stable thermodynamically in the absence of an environment. Although 4-methylene-2-azetidinone is the most stable product of the ketene-vinylimine cycloaddition, its activation barrier is higher than that for 4-methylene-2-iminooxetane by ca. 6 kcal/mol. Therefore, the latter product can be obtained owing to kinetic control. The activation barriers in the allene-isocyanic acid reactions are quite high, 50-70 kcal/mol, whereas in the course of the ketene-vinylimine cycloaddition they are equal to ca. 30-55 kcal/mol. All the reactions studied were found to be concerted and mostly asynchronous. Simulation of the solvent environment (toluene, tetrahydrofuran, acetonitrile, and water) by using Tomasi's polarized continuum model with the integral equation formalism (IEF-PCM) method showed the allene-isocyanic reactions remained concerted, yet the activation barriers were somewhat ...Continue Reading

References

Sep 11, 1999·Bioorganic & Medicinal Chemistry·W W OgilvieR Déziel
Jan 10, 2002·Chemical Reviews·Yves DejaegherNorbert De Kimpe
Nov 8, 2003·The Journal of Organic Chemistry·Jesús Rodríguez-OteroAngeles Peña-Gallego
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Jul 21, 2006·The Journal of Physical Chemistry. B·Silvia FratiloiuLaurens D A Siebbeles

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Citations

Oct 1, 2013·Journal of Molecular Modeling·Xueli ChengYongjun Liu
Jun 19, 2013·Chemical Reviews·Annette D Allen, Thomas T Tidwell
Dec 15, 2015·The Journal of Organic Chemistry·Carlos Silva LópezDieter Cremer
Oct 7, 2015·Chemistry : a European Journal·Luis CasarrubiosMiguel A Sierra
Jul 30, 2016·Chemical Communications : Chem Comm·Benito AlcaideTeresa Martínez Del Campo
Jan 15, 2009·Journal of the American Chemical Society·Hua JiDavid M Birney
Oct 11, 2016·The Journal of Physical Chemistry. a·José Enrique Barquera-Lozada
Oct 22, 2013·Organic & Biomolecular Chemistry·Margarita M VallejosSilvina C Pellegrinet
Oct 2, 2009·The Journal of Physical Chemistry. a·Gaddamanugu Gayatri, G Narahari Sastry
Dec 1, 2017·The Journal of Organic Chemistry·David M Lemal

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