Multiple Mechanisms for the Thermal Decomposition of Metallaisoxazolin-5-ones from Computational Investigations

作者：Zhou Chen Chen; Hawthorne M Frederick; Houk K N^*; Jimenez Oses Gonzalo^*

来源：Journal of Organic Chemistry, 2017, 82(16): 8438-8443.

DOI：10.1021/acs.joc.7b01169

The thermal decompositions of metallaisoxazolin-5-ones containing Ir, Rh, or Co are investigated using density functional theory. The experimentally observed decarboxylations of these molecules are found to proceed through retro-(3+2)-cycloaddition reactions, generating the experimentally reported,72 side-bonded nitrile complexes. These intermediates can isomerize in situ to yield a eta(1) nitrile complex. A competitive alternative pathway is also found where the decarboxylation happens concertedly with an aryl migration process, producing a eta(1) isonitrile complex. Despite their comparable stability, these eta(2) bonded species were not detected experimentally. The experimentally detected eta(2) side bound species are likely subsequent C-H activation reactions with hydrocarbon solvents reported for some of these metallaisoxazolin-5-ones.

• 出版日期2017-8-18