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Reactivity of (Mono‐ tert ‐butyloxiranyl)lithium: A Theoretical Ab Initio Study
Author(s) -
Bouyacoub Abdelatif,
HadjadjAoul Ratiba,
Volatron François
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800457
Subject(s) - chemistry , reactivity (psychology) , ab initio , lithium (medication) , carbene , computational chemistry , solvation , molecule , catalysis , organic chemistry , medicine , alternative medicine , pathology , endocrinology
The reactivity of the lithiated tert ‐butyloxiranyl anion has been studied by means of ab initio calculations at the CCSD(T)//MP2 level of theory. Four reaction paths have been studied (three ring‐opening reactions and one addition reaction). All extrema were located and characterised. The effects of solvation by one or two MeLi molecules were studied for each reaction path by reoptimising the various extrema. It was found that the addition reaction path becomes competitive when at least two MeLi molecules are taken into account. This shows the catalytic effect of alkyllithium on this reaction path. In no case could a free carbene be characterised as a reaction intermediate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)