Enantioenrichment by Iterative Retro-Aldol/Aldol reaction catalyzed by an achiral or racemic base

Chemistry - A European Journal

Volumn 16, Issue 13, 2010, Pages 3918-3921

  Flock, Angelika M ^a   Reucher, Christine M M ^a   Bolm, Carsten ^a  

^a RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

Aldol reaction; Asymmetric amplification enantioenrichment; Grinding; Reversible reactions

Indexed keywords

ALDOL REACTIONS; ASYMMETRIC AMPLIFICATION; CHEMICAL EQUATIONS; REACTION CATALYZED; REVERSIBLE REACTION;

CHEMICAL REACTIONS; GRAIN BOUNDARIES; GRINDING (COMMINUTION); GRINDING (MACHINING);

AMPLIFICATION;

EID: 77950196940     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200903497     Document Type: Article

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43. Use of piperidine instead of pyrrolidine raised the e.r. of anti-1 from 85:15 to 95:5:4.5 after 1 d. It reached an e.r. of 97.5:2.5 after 4 d.
44. 1H NMR showed that 74 and 83%, respectively, of anti-1 had been converted to the corresponding syn-aldol products. The stereochemical assignments of the resulting syn-1 indicated unchanged ee values of 30 and 70%, respectively, and suggested that the major products had 2R,4S,1'.R- configuration. These results can be interpreted as indication for a selective solution phase epimerization of anti-1 at C2 to give syn-1. Subsequent investigations of this interesting "destructive conversion" of stereoisomers in solution shall, reveal to what extend this phenomenon is responsible for the observed e.r. change in the original experiments.
45. Tsogoeva proposed that the enantiomerization process involved the formation of an enamine intermediate in solution and a chemisorption of the other reactant (in their case an imine) on the crystal, surface of the major enantiomer (ref. [17b]). As a result, the major enantiomer is reproduced at the crystal/solution interface in an autocatalytic fashion. A racemic compound could reproduce itself in the same mode. It is not clear, however, how compound mixtures will behave. The formation of racemic anti-S in our competition experiments seems to indicate that the crystal surface of anti-1 does not affect the stereochemical path of the anti-S formation.
46. The reaction was conducted under the conditions of the competition experiment (with DMSO as solvent and 2.4equiv of cyclohexanone). Without cyclohexanone, the ee was lower to give anti-S with a residual e.r. of 81.5:185.
47. While this manuscript was under review, we learned about an organocatalytic asymmetric retro aldol reaction catalyzed by a chiral diamine triflic acid adduct which has been utilized in efficient kinetic resolutions (as reported by Professor Dr. S. Luo at Symposium on Catalysis and Fine Chemicals (C&FC) 2009 in Seoul, on December 1.5, 2009). We thank Professor Luo for sending us subsequently an unpublished summary of his work.