New chiral calixsalen chromium complexes: recyclable asymmetric catalysts.

A chiral N,N'-bis(salicylidene)ethylenediamine (salen) polymer has been prepared by a condensation reaction between a thiophenedisalicyladehyde derivative and (S,S)-cyclohexane-1,2-diamine. This polymeric compound was demonstrated to possess a cyclic structure with two to five repetitive units. The addition of chromium(II) salts led to the generation of a chiral catalyst that could be recovered as an insoluble powder. The performance of this new calixsalen-type catalyst was examined in various transformations, particularly in its ability to promote nucleophilic epoxide ring opening under heterogeneous conditions. The target products were obtained in high yields and with improved selectivity compared with those obtained by using analogous linear polymers. The arrangement of the catalytic sites in the cyclic structure is probably more suitable for the necessary cooperative bimetallic pathway of this demanding reaction. The catalyst could be successfully recycled. This approach represents the first use of calixsalen complexes under heterogeneous catalytic conditions.

Recoverable chiral salen complexes for asymmetric catalysis: recent progress.

Chiral salen-type complexes have already been proven to be particularly useful asymmetric catalysts for the preparation of a wide range of enantioenriched products. Research for efficient recovery and recycling of such complexes is ongoing and has already demonstrated the value of these procedures in terms of atom economy and overall economical savings. Results reported in the near past (2006-2009) dealing with the use of recyclable chiral salen complexes are summarized here, classified according to the type of heterogenization procedures involved.

Original use of the same heterogeneous chiral catalyst batch to promote different asymmetric reactions.

An electrogenerated heterogeneous chiral (poly)salen-thiophene chromium complex successfully promoted different asymmetric catalytic reactions in an original successive manner, demonstrating its high stability and versatility.

Amino acid homologation by the Blaise reaction: a new entry into nitrogen heterocycles.

A general strategy for the amino acid homologation via Blaise reaction and subsequent reduction is presented. This strategy involves the preparation of protected alpha-amino nitriles from the corresponding amino acids, followed by the zinc-mediated condensation of tert-butyl bromoacetate, to give the imidazolidones after iminozincate cyclization. Reduction gave the saturated imidazolidinones with cis or trans stereochemistry, depending on the reduction conditions. This strategy was applied to nonfunctionalized amino acids and to functionalized amino acids such as serine and aspartic acid. Additionally, acidic hydrolysis of cis or trans imidazolidinones to the corresponding chiral 4-aminopyrrolidones is described.

New chiral thiophene-salen chromium complexes for the asymmetric Henry reaction.

Chiral thiophene-salen chromium complexes were investigated in their monomeric form as soluble catalysts in the enantioselective Henry reaction of several aldehydes. The anodic polymerization of one complex led to an insoluble powder that was successfully used as a heterogeneous catalyst for the transformation of 2-methoxybenzaldehyde with enantiomeric excesses up to 77%. The polymerized catalyst was recovered and also recycled in an original multisubstrate procedure.