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Volumn 15, Issue 33, 2009, Pages 8251-8258

Systematic studies using 2-(1-adamantylethynyl)pyrimidine-5-carbaldehyde as a starting material in soai's asymmetric autocatalysis

Author keywords

Amplification; Asymmetr c; Autocatalysis; Chirality; Organozinc reagents; Systems chemistry

Indexed keywords

AUTOCATALYSIS; BACK CALCULATION; ENANTIOMERIC EXCESS; MECHANISTIC STUDIES; ORGANOZINC REAGENTS; REACTION CONDITIONS; REACTION CYCLES; REACTION PARAMETERS; STARTING MATERIALS; SYSTEMATIC STUDY; SYSTEMS CHEMISTRY;

EID: 68949101681     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200900634     Document Type: Article
Times cited : (31)

References (78)
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    • The term asymmetric autocatalytic activity is not precisely defined. We use it in the sense that the higher the ee enhancement of a given system under identical starting conditions the higher is the asymmetric autocatalytic activity. A systematic approach to a possible parameter characterizing asymmetric autocatalytic activity is given in a M. Maioli, K. Micskei, L. Caglioti, C. Zucchi, G. Pályi, J. Math. Chem. 2008, 43, 1505-1515;
    • The term asymmetric autocatalytic activity is not precisely defined. We use it in the sense that the higher the ee enhancement of a given system under identical starting conditions the higher is the asymmetric autocatalytic activity. A systematic approach to a possible parameter characterizing asymmetric autocatalytic activity is given in a) M. Maioli, K. Micskei, L. Caglioti, C. Zucchi, G. Pályi, J. Math. Chem. 2008, 43, 1505-1515;
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    • 2 is mentioned, however, the author did not state which residue R in 1 was used tor the studies presented;
    • 2 is mentioned, however, the author did not state which residue R in 1 was used tor the studies presented;
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    • a short overview of the current knowledge on a possible mechanism is given
    • i) a short overview of the current knowledge on a possible mechanism is given
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    • in section 5.1 in T. Satyanarayana, S. Abraham, H. B. Kagan, Angew. Chem. 2009, 121, 464-503;
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    • The yield-time dependency was investigated in one experiment at -45°;C and in two different experiments at 0°C (no results on observed ee values reported) in I. Sato, D. Omiya, K. Tsukiyama, Y. Ogi, K. Soai, Tetrahedron: Asymmetry 2001, 12, 1965-1969;
    • a) The yield-time dependency was investigated in one experiment at -45°;C and in two different experiments at 0°C (no results on observed ee values reported) in I. Sato, D. Omiya, K. Tsukiyama, Y. Ogi, K. Soai, Tetrahedron: Asymmetry 2001, 12, 1965-1969;
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    • results from three experiments at -25°C are reported in I. Sato, D. Omiya, H. Igarashi, K. Kato, Y. Ogi, K. Tsukiyama, K. Soai, Tetrahedron: Asymmetry 2003, 14, 975-979.
    • b) results from three experiments at -25°C are reported in I. Sato, D. Omiya, H. Igarashi, K. Kato, Y. Ogi, K. Tsukiyama, K. Soai, Tetrahedron: Asymmetry 2003, 14, 975-979.
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    • Time-oscillating ee values could also be obtained as theoretically studied in K. Micskei, G. Rábai, E. Gál, L. Caglioti, G. Pályi, J. Phys. Chem. B 2008, 112, 9196-9200.
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    • Concerning the topic of precipitation in the Soai reaction, extensive studies have been performed, see
    • Concerning the topic of precipitation in the Soai reaction, extensive studies have been performed, see: F. G. Buono, H. Iwamura, D. G. Blackmond, Angew. Chem. 2004, 116, 2151-2155;
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    • Angew. Chem. Int. Ed. 2004, 43, 2099-2103. It has to be noted that, during our studies, in the majority of the reaction tubes a milky product solution was obtained. Except for extreme temperatures and high catalyst concentrations, the clouding mostly occurred after a considerable reaction time (one to several hours; monitoring by TLC and HPLC showed that the clouding appeared after the reactions were completed). A considerable number of our reactions stayed clear throughout. We observed no correlation between this fact and the enhancement of ee in our study.
    • Angew. Chem. Int. Ed. 2004, 43, 2099-2103. It has to be noted that, during our studies, in the majority of the reaction tubes a milky product solution was obtained. Except for extreme temperatures and high catalyst concentrations, the clouding mostly occurred after a considerable reaction time (one to several hours; monitoring by TLC and HPLC showed that the clouding appeared after the reactions were completed). A considerable number of our reactions stayed clear throughout. We observed no correlation between this fact and the enhancement of ee in our study.
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    • These low catalyst concentrations are prepared by dilution of a stock solution handled with utmost care and have to be considered as theoretical concentrations. Due to adsorption phenomena the real concentration could be different
    • These low catalyst concentrations are prepared by dilution of a stock solution handled with utmost care and have to be considered as theoretical concentrations. Due to adsorption phenomena the real concentration could be different.
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    • In reference [9d] the authors state, It should also be noted that this system displays condition-dependent complexities. Contribution from a slow but significant background reaction triggering racemic autocatalysis may be minimized only by employing higher catalyst concentrations. Our findings suggest that this conclusion is not true in general, but only for enantiopure catalyst 1d as used in reference [9b
    • In reference [9d] the authors state, "It should also be noted that this system displays condition-dependent complexities. Contribution from a slow but significant background reaction triggering racemic autocatalysis may be minimized only by employing higher catalyst concentrations." Our findings suggest that this conclusion is not true in general, but only for enantiopure catalyst 1d as used in reference [9b].
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    • There are no data available on the influence of the concentration of a low ee catalyst for substrates 1 a-1 f.
    • There are no data available on the influence of the concentration of a low ee catalyst for substrates 1 a-1 f.
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    • The addition of rac-2g is not necessary for spontaneous symmetry breaking. If no catalyst was added at all, spontaneous symmetry breaking yielding (R)- and (S)-2g was also observed in preliminary experiments; this will be subject of ongoing research.
    • The addition of rac-2g is not necessary for spontaneous symmetry breaking. If no catalyst was added at all, spontaneous symmetry breaking yielding (R)- and (S)-2g was also observed in preliminary experiments; this will be subject of ongoing research.
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    • For an overview of chiral initiators, see:, Ed, K. Soai, Springer, Berlin
    • For an overview of chiral initiators, see: K. Soai, T. Kawasakin, Topics in Current Chemistry, Vol. 284 (Ed.: K. Soai), Springer, Berlin, 2008, pp. 11-21.
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    • Soai, K.1    Kawasakin, T.2
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    • Procedure from reference [5b] (personal communication from P. Knochel mentioned in this work).
    • Procedure from reference [5b] (personal communication from P. Knochel mentioned in this work).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.