Fluorine as a Regiocontrol Element in the Ring Opening of Bicyclic Aziridiniums

The origin of the variation in the regioselectivity of the nucleophilic ring opening of a series of bicyclic aziridinium ions derived from N‐alkylprolinols was investigated by quantum‐chemical computations (M06‐2X/6‐31+G(d,p)‐SMD). These aziridiniums differ only in the degree and the configurations...

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Bibliographic Details
Published inHelvetica chimica acta Vol. 95; no. 11; pp. 2265 - 2277
Main Authors Lam, Yu-hong, Houk, Kendall N., Cossy, Janine, Gomez Pardo, Domingo, Cochi, Anne
Format Journal Article
LanguageEnglish
Published Zürich WILEY-VCH Verlag 01.11.2012
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
Subjects
Aziridinium
Computational chemistry
Fluorine
gauche Effect
Nitrogen heterocycles
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Summary:The origin of the variation in the regioselectivity of the nucleophilic ring opening of a series of bicyclic aziridinium ions derived from N‐alkylprolinols was investigated by quantum‐chemical computations (M06‐2X/6‐31+G(d,p)‐SMD). These aziridiniums differ only in the degree and the configurations of F‐substitution at C(4). With the azide ion as nucleophile, the ratio of the piperidine to the pyrrolidine product was computed. An electrostatic gauche effect influences the conformation of the adjoining five‐membered ring in the fluorinated bicyclic aziridinium. This controls the regioselectivity of the aziridinium ring opening.
Bibliography:ArticleID:HLCA201200461
ark:/67375/WNG-2PLQXS0G-B
istex:512D683E6E8B20FE691CFABEFDA01FA06DB676D3
ISSN:0018-019X
1522-2675
DOI:10.1002/hlca.201200461