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Stereoselective Aldol Addition to Rhenium(I) Complexes and Reversible Dimerization with Epimerization of the Metal Center
Author(s) -
Álvarez Celedonio M.,
Carrillo Romen,
GarcíaRodríguez Raúl,
Miguel Daniel
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300412
Subject(s) - rhenium , epimer , aldol reaction , stereoselectivity , center (category theory) , metal , chemistry , stereochemistry , medicinal chemistry , crystallography , organic chemistry , catalysis
Herein, we report several examples of stereoselective aldol additions of aldehydes or ketones to Re I tricarbonyl complexes to form monomeric derivatives in good yields. The metal‐centered chirality defines the final stereochemistry of the carbon atom of the monomeric Re I complex after the addition. However, it cannot control the resulting stereochemistry of the enolate part, and thus, if the α‐carbon atom of the reagent is prochiral, a mixture of diastereoisomers is obtained. On the other hand, all of the monomeric complexes can be reversibly dimerized in basic media to form cis dimers, for which an epimerization of the metal‐centered chirality is required in order to avoid steric congestion. All of these results are supported by exhaustive crystallographic analysis.