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Volumn 46, Issue 3, 2007, Pages 393-396

Evidence of asymmetric autocatalysis in organocatalytic reactions

Author keywords

Asymmetric autocatalysis; Density functional calculations; Mannich reaction; Organocatalysis; Transition states

Indexed keywords

CATALYSTS; HYDROGEN BONDS; PHASE EQUILIBRIA; SUBSTRATES;

EID: 33846529045     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200603517     Document Type: Article
Times cited : (88)

References (26)
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    • 0036084410 scopus 로고    scopus 로고
    • for a review, see
    • e) for a review, see: K. Soai, I. Sato, Chirality 2002, 14, 548.
    • (2002) Chirality , vol.14 , pp. 548
    • Soai, K.1    Sato, I.2
  • 11
  • 18
    • 33846519040 scopus 로고    scopus 로고
    • We cannot preclude that the product may have played a role during its formation in the presence of proline as well
    • We cannot preclude that the product may have played a role during its formation in the presence of proline as well.
  • 19
    • 33846518482 scopus 로고    scopus 로고
    • To assess the effect of asymmetric induction, we have also included the reduced ee values of the product (eep) after deduction of the effect of the initial catalyst on the ee values of the isolated product: eep, n1/(n1-no))·eep′, no·eeo//n1, with eeo, ee value of the initially added product catalyst, eep′, observed ee value of isolated product, no, product initially added [mol, n1, total isolated product [mol
    • 1 = total isolated product [mol].
  • 20
    • 33846471319 scopus 로고    scopus 로고
    • 2 and toluene as solvents. While the reaction in toluene gave only traces of product, the yield in methylene chloride was 4-6 % with an ee value of the isolated product close to that of the initially added product (98 % ee).
    • 2 and toluene as solvents. While the reaction in toluene gave only traces of product, the yield in methylene chloride was 4-6 % with an ee value of the isolated product close to that of the initially added product (98 % ee).
  • 21
    • 33846473301 scopus 로고    scopus 로고
    • Traces of p-methoxyaniline have been detected after workup. Unused starting material could be retrieved in all experiments, that is, the reaction does not proceed to completion.
    • Traces of p-methoxyaniline have been detected after workup. Unused starting material could be retrieved in all experiments, that is, the reaction does not proceed to completion.
  • 22
    • 33846553250 scopus 로고    scopus 로고
    • After keeping the product 3 for one month at -21°C, we observed a decrease in enantiomeric purity from 98 % ee to 53 % ee. However, no loss of enantiomeric purity was observed after 4 days at room temperature.
    • After keeping the product 3 for one month at -21°C, we observed a decrease in enantiomeric purity from 98 % ee to 53 % ee. However, no loss of enantiomeric purity was observed after 4 days at room temperature.
  • 23
    • 0034750244 scopus 로고    scopus 로고
    • For reviews on asymmetric aminocatalysis, see: a
    • For reviews on asymmetric aminocatalysis, see: a) B. List, Synlett 2001, 1675;
    • (2001) Synlett , pp. 1675
    • List, B.1
  • 25
    • 33846489224 scopus 로고    scopus 로고
    • + may indicate the formation of a product-substrate complex.
    • + may indicate the formation of a product-substrate complex.
  • 26
    • 33846486994 scopus 로고    scopus 로고
    • Gaussian03, Revision A.11.4, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, N. Rega, P. Salvador, J. J. Dannenberg, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc, Pittsburgh PA, 2002
    • Gaussian03, Revision A.11.4, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, N. Rega, P. Salvador, J. J. Dannenberg, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh PA, 2002.


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