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We have carried out a similar experiment with the Michael product from the reaction of trans-β-nitrostyrene and acetone with either added pyrrolidine or DBU. After 12 days we observed asymmetric depletion in the product slurry with DBU (from 17.3 to 11.0% ee) but asymmetric amplification (from 17.3 to 20.4% ee) with pyrrolidine
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We have carried out a similar experiment with the Michael product from the reaction of trans-β-nitrostyrene and acetone with either added pyrrolidine or DBU. After 12 days we observed asymmetric depletion in the product slurry with DBU (from 17.3 to 11.0% ee) but asymmetric amplification (from 17.3 to 20.4% ee) with pyrrolidine.
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Asakura, studying a system crystallizing from the unstirred supercooled melt, assumed that secondary nucleation resulted from the spontaneous formation of chiral clusters from the melt in the vicinity of the bulk crystal surface, see reference [12] and K. Asakura, Y. Nagasaka, M. Hidaka, M. Hayashi, S. Osanai, D. K. Kondepudi, Chirality 2004, 16, 131.
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Asakura, studying a system crystallizing from the unstirred supercooled melt, assumed that "secondary nucleation" resulted from the spontaneous formation of chiral clusters from the melt in the vicinity of the bulk crystal surface, see reference [12] and K. Asakura, Y. Nagasaka, M. Hidaka, M. Hayashi, S. Osanai, D. K. Kondepudi, Chirality 2004, 16, 131.
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For very low or even zero solution-phase enantiomerization rates, phase disproportionation of enantiomers might become an additional factor. Furthermore, factors that govern the solubility of the conglomerate (like the nature of solvent and the temperature, see for example references [17b] and [30]) could also crucially affect the effectiveness of the transformation.
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For very low or even zero solution-phase enantiomerization rates, phase disproportionation of enantiomers might become an additional factor. Furthermore, factors that govern the solubility of the conglomerate (like the nature of solvent and the temperature, see for example references [17b] and [30]) could also crucially affect the effectiveness of the transformation.
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The preferential enrichment of racemic compounds by a polymorphic transition involves a near enantiopure solution, in contrast to the observations for our system, see
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While this manuscript was under review, a paper was submitted which describes a mechanism for the generation of homochirality by grinding and an autocatalytic enantiomerization at the crystal surface Y.Saito, H. Hyuga, J. Phys. Soc. Jpn. 2008, DOI: arXiv:0810.0910v1
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While this manuscript was under review, a paper was submitted which describes a mechanism for the generation of homochirality by grinding and an autocatalytic enantiomerization at the crystal surface Y.Saito, H. Hyuga, J. Phys. Soc. Jpn. 2008, DOI: arXiv:0810.0910v1.
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The method described herein might be compared with the recently demonstrated symmetry breaking in homogenous reversible reactive systems closed to matter flow, see: M. Mauksch, S. B. Tsogoeva, S.-W. Wei, I. M. Martynova, Chirality 2007, 19, 816
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The method described herein might be compared with the recently demonstrated symmetry breaking in homogenous reversible reactive systems closed to matter flow, see: M. Mauksch, S. B. Tsogoeva, S.-W. Wei, I. M. Martynova, Chirality 2007, 19, 816.
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