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Volumn 48, Issue 3, 2009, Pages 590-594

Generation of highly enantioenriched crystalline products in reversible asymmetric reactions with racemic or achiral catalysts

Author keywords

Asymmetric amplification; Chiral resolution; Chirality; Crystal growth; Nucleophilic addition reactions

Indexed keywords

ADDITION REACTIONS; CATALYSIS; CATALYSTS; CHEMICAL ENGINEERING; CHEMICAL REACTIONS; CHIRALITY; CRYSTAL GROWTH; CRYSTALLIZATION; DISSOLUTION; ENANTIOMERS; GRAIN BOUNDARIES; GROWTH (MATERIALS); STEREOCHEMISTRY;

EID: 58249124556     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200803877     Document Type: Article
Times cited : (108)

References (58)
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    • The Viedma experiment has been interpreted by Uwaha, employing a kinetic model in computer simulations and involving minimal chiral units, see
    • The Viedma experiment has been interpreted by Uwaha, employing a kinetic model in computer simulations and involving "minimal chiral units", see: M. Uwaha, J. Phys. Soc. Jpn. 2004, 73, 2601.
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    • In a recent theoretical study, we showed that linear autocatalysis in a closed microreversible recycling network can result in fully chiral stationary-state solutions in open-flow and homogenous systems, see: M. Mauksch, S. B. Tsogoeva, ChemPhysChem 2008, 9, 2359;
    • a) In a recent theoretical study, we showed that linear autocatalysis in a closed microreversible recycling network can result in fully chiral stationary-state solutions in open-flow and homogenous systems, see: M. Mauksch, S. B. Tsogoeva, ChemPhysChem 2008, 9, 2359;
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    • for a similar mechanism, which employs an irreversible recycling activation step fuelled by an external energy source, see:, DOI: 10.1021/jp803588z
    • b) for a similar mechanism, which employs an irreversible recycling activation step fuelled by an external energy source, see: R. Plasson, J. Phys. Chem. B 2008, DOI: 10.1021/jp803588z.
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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
    • 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.
  • 54
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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.
    • 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.
    • 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
    • The "preferential enrichment" of racemic compounds by a polymorphic transition involves a near enantiopure solution, in contrast to the observations for our system, see: R. Tamura, H. Takahashi, U. Takanori, J. Chem. Soc. Jpn. 2001, 2, 71.
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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
    • 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
    • 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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.