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Issue 18, 2018
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Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor–acceptor interactions

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Abstract

This paper describes a mechanistic study, with the interplay of experiment and theory, on the cycloadditions of a bicyclic mesoionic 1,3-dipole versus a series of representative symmetrical (1-phenyl-1H-pyrrole-2,5-dione and dimethyl maleate) and asymmetrical [(E)-(2-nitrovinyl)benzene, acrylonitrile, and but-3-en-2-one] olefinic dipolarophiles. These results allow a comparative analysis with monocyclic dipoles and open further avenues to structurally diversified heteroatom-rich rings. The unichiral version of the bicyclic dipole leads to adducts containing up to five chiral centers, whose formation proceeds with high levels of facial stereoinduction in reactions involving bulky dipolarophiles. The second and largest part of this study provides a theoretical interrogation on the pericyclic mechanism with DFT-methods [M06-2X/6-311++G(d,p)]. In order to get further mechanistic insights, we have also explored charge transfers between reaction partners using NBO analysis, which satisfactorily justifies the stereochemical outcome.

Graphical abstract: Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor–acceptor interactions

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Publication details

The article was received on 20 Mar 2018, accepted on 11 Apr 2018 and first published on 11 Apr 2018


Article type: Paper
DOI: 10.1039/C8OB00683K
Citation: Org. Biomol. Chem., 2018,16, 3438-3452
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    Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor–acceptor interactions

    J. García de la Concepción, M. Ávalos, P. Cintas, J. L. Jiménez and M. E. Light, Org. Biomol. Chem., 2018, 16, 3438
    DOI: 10.1039/C8OB00683K

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