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Article Dans Une Revue Organic Letters Année : 2023

Bending Enamine Patterns of Stabilized Pentalenes into “Polymethine Ylides”

Résumé

We report the synthesis and structural study of 2-substituted 1,3-bis(dimethylamino)pentalenes. The two-electrons donating substituents shift the formally anti-aromatic pattern toward more suited polarized structures. A subtle steric trade off can result either in planar cyclopentadienyl vinamidiniums, or in distorted structures featuring a pyramidalized ylidic carbon adjacent to a stabilized p-conjugated iminium (polymethine). This latter pattern mimics a postulated activated distorted geometry for key Breslow intermediates in the active site of thiamine-dependent enzymes. It highlights how the energetic drive to avoid anti-aromaticity can be used to access models for unconventional distorted conformations of organic molecules.

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Chimie
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hal-04234557 , version 1 (10-10-2023)

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Valentin Thery, Cyriac Barra, Alexandra Simeoni, Jacques Pecaut, Eder Tomás-Mendivil, et al.. Bending Enamine Patterns of Stabilized Pentalenes into “Polymethine Ylides”. Organic Letters, 2023, 25 (3), pp.560-564. ⟨10.1021/acs.orglett.3c00037⟩. ⟨hal-04234557⟩
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