Document Detail


Lewis Acid Catalysed Reactions of Chiral Imidazolidinones and Oxazolidinones: Insights on the Role of the Catalyst.
MedLine Citation:
PMID:  21786834     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The mechanism proposed by Evans to justify the selectivity obtained in Lewis acid catalysed Diels-Alder reactions of cyclopentadiene with acyloxazolidinones has been generalized and used in the rationalization of selectivities obtained in many other systems. However, we recently proposed an alternative mechanism, on the basis of open-chain mono and bicomplexes, that avoids the need for chelates and explains the selectivity obtained by Evans. In this manuscript we apply our proposal to the catalysed conjugated addition of amines to acylimidazolidinones, reported by Cardillo, and we clearly show that aluminium chelates are not involved in the reaction, as they induce no selectivity, while Cardillo observed high experimental selectivities. Our data equally show that bicomplexes with carbonyl parallel orientation, proposed by Cardillo to justify the experimental selectivity with non-chelating Lewis acids, indeed induce the opposite selectivity and have also to be dismissed. On the other hand, our mechanistic proposal allows for the full rationalization of the data obtained by Cardillo with aluminium, boron or zinc Lewis acids, and supports our previous proposal on DA cycloadditions of dienes to Evans chiral auxiliary derivatives.
Authors:
Filipe J S Duarte; Snezhana M Bakalova; Eurico J Cabrita; António Gil Santos
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2011-7-26
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  -     ISSN:  1520-6904     ISO Abbreviation:  -     Publication Date:  2011 Jul 
Date Detail:
Created Date:  2011-7-26     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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