aldol reactions

Copper Complexes in the Promotion of Aldol Addition to Pyridine-2-carboxaldehyde: Synthesis of Homo- and Heteroleptic Complexes and Stereoselective Double Aldol Addition
Lucía Álvarez-Miguel, Héctor Barbero, Adriana Sacristán-Martín, José M. Martín Álvarez, Alfonso Pérez-Encabo, Celedonio M. Álvarez, Raúl García-Rodríguez*, Daniel Miguel*
Inorg. Chem., 2018, 57, 264-276. DOI: 10.1021/acs.inorgchem.7b02448

A general and simple one-pot procedure for the aldol addition to Cu(II) complexes is reported. The method accesses novel Cu complexes with a large variety of different structural motifs, from which the aldol-addition ligand can be liberated by treatment with NH3. A regio- and stereoselective double aldol addition of pyca in which the novel double aldol addition product acts as a pentadentate ligand is also described.

Stereoselective Aldol Addition to Re(I) Complexes and Reversible Dimerization with Epimerization of the Metal Center
Celedonio M. Álvarez, Romen Carrillo, Raúl García-Rodríguez, Daniel Miguel
Chem. Eur. J., 2013, 19, 8285-8293. DOI: 10.1002/chem.201300412

Scheme for TOCb
Facing up to Re: The stereochemical pathways of the stereoselective aldol addition of carbonyl compounds to ReI complexes and pH-driven dimerizations of these adducts (see scheme; Tf=trifluoromethanesulfonyl) have been studied by crystallographic analysis. The aldol addition only occurs on one face of the carbonyl compound, whereas the dimerization occurs with a concomitant epimerization of the metal center.


pH-driven dynamic stereoinduction: epimerization upon dimerization in rhenium(I) complexes.
Celedonio M. Álvarez, Romen Carrillo, Raúl García-Rodríguez and Daniel Miguel
Chem Commun., 2011, 47, 12765-12767. DOI: 10.1039/C1CC14799D.

chemcomm GA

Basic conditions lead to dimerization of a Re(I) complex and concomitantly to an epimerization of the metal centre. The process is reversible upon acid addition.

This communnication was given the inside cover of Chem Comm. 2011, 47, issue 48