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Volumn 16, Issue 10, 2010, Pages 3147-3156

Mechanism of the asymmetric autocatalytic soai reaction studied by density functional theory

Author keywords

Asymmetric amplification; Autocatalysis; Density functional calculations; Reaction mechanisms; Soai reaction

Indexed keywords

ASYMMETRIC AMPLIFICATION; AUTOCATALYTIC; CATALYTIC CYCLES; CHIRAL AMPLIFICATION; DENSITY-FUNCTIONAL CALCULATIONS; DOMINANT MECHANISM; ENANTIOSELECTIVE; HOMOCHIRAL DIMERS; REACTION MECHANISM;

EID: 77649204528     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200902543     Document Type: Article
Times cited : (40)

References (78)
  • 2
  • 9
    • 52049090428 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2008, 47, 6445-6447;
    • (2008) Angew. Chem. Int. Ed. , vol.47 , pp. 6445-6447
  • 11
    • 53249125961 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2008, 47, 7226-7229:
    • (2008) Angew. Chem. Int. Ed. , vol.47 , pp. 7226-7229
  • 14
  • 16
    • 70349782335 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2009, 48. 3278-3280:
    • (2009) Angew. Chem. Int. Ed. , vol.48 , pp. 3278-3280
  • 18
    • 70349784853 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2009, 48, 4581-4583.
    • (2009) Angew. Chem. Int. Ed. , vol.48 , pp. 4581-4583
  • 20
    • 0039497477 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 1999, 38. 2199-2201:
    • (1999) Angew. Chem. Int. Ed. , vol.38 , pp. 2199-2201
  • 23
    • 70349898692 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2009, 48, 5869-5871;
    • (2009) Angew. Chem. Int. Ed. , vol.48 , pp. 5869-5871
  • 46
    • 4744354453 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2004. 43, 4884-4887:
    • (2004) Angew. Chem. Int. Ed. , vol.43 , pp. 4884-4887
  • 52
    • 53249103664 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2008, 47, 6832-6835.
    • (2008) Angew. Chem. Int. Ed. , vol.47 , pp. 6832-6835
  • 53
    • 0001678004 scopus 로고
    • The importance of hetero versus homochiral dimers for nonlinear effects in organozinc additions has been intensively investigated, both experimentally and computationally: a M. Kitamura, S. Suga, M. Niwa, R. Noyori, J.
    • The importance of hetero versus homochiral dimers for nonlinear effects in organozinc additions has been intensively investigated, both experimentally and computationally: a) M. Kitamura, S. Suga, M. Niwa, R. Noyori, J. Am. Chem. Soc. 1995, 117, 4832-4842;
    • (1995) Am. Chem. Soc. , vol.117 , pp. 4832-4842
  • 57
    • 0032538773 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 1998, 37, 2922-2959;
    • (1998) Angew. Chem. Int. Ed. , vol.37 , pp. 2922-2959
  • 63
  • 65
    • 68949101681 scopus 로고    scopus 로고
    • A cautionary note is in order here, since new accurate experimental results regarding the reaction of 2-(1-adamantylethynyl)-pyrimidine5- carbaldehyde, published by Gehring et al. while ref. [12] was in press, could lead to a re-evaluation of the nature of the resting state in the Soai reaction as a function of substrate, temperature, and other experimental conditions: M. Busch, M. Schlageter, D. Weingand, T. Gehring
    • A cautionary note is in order here, since new accurate experimental results regarding the reaction of 2-(1-adamantylethynyl)-pyrimidine5- carbaldehyde, published by Gehring et al. while ref. [12] was in press, could lead to a re-evaluation of the nature of the resting state in the Soai reaction as a function of substrate, temperature, and other experimental conditions: M. Busch, M. Schlageter, D. Weingand, T. Gehring, Chem. Eur. J. 2009, 15, 8251-8258.
    • (2009) Chem. Eur. J. , vol.15 , pp. 8251-8258
  • 67
    • 77649224263 scopus 로고    scopus 로고
    • The M05-2X functional implicitly accounts for "medium-range" electron correlation because of the way in which it is parametrized. This is sufficient to describe the dispersion interactions within many complexes, apart from hydrogen-bonded systems, in which much of the dispersion interaction is "long-range" (>5 Å). E. G. Hohenstein, S. T. Chill, C. D. Sherrill
    • The M05-2X functional implicitly accounts for "medium-range" electron correlation because of the way in which it is parametrized. This is sufficient to describe the dispersion interactions within many complexes, apart from hydrogen-bonded systems, in which much of the dispersion interaction is "long-range" (>5 Å). E. G. Hohenstein, S. T. Chill, C. D. Sherrill, J. Chem. Theory Comput. 2008, 4, 19962000.
    • (2008) J. Chem. Theory Comput. , vol.4 , pp. 19962000
  • 71
    • 77649213978 scopus 로고    scopus 로고
    • Computational details, optimized geometries and energies obtained with the program. Gaussian 03 are reported in the Supporting Information
    • a) Computational details, optimized geometries and energies obtained with the program. Gaussian 03 are reported in the Supporting Information;
  • 73
    • 77649205018 scopus 로고    scopus 로고
    • This conclusion can be deduced by the observation of a secondorder dependency of the reaction rate on the aldehyde concentration coupled with the observation of a relatively low free energy of activation
    • This conclusion can be deduced by the observation of a secondorder dependency of the reaction rate on the aldehyde concentration coupled with the observation of a relatively low free energy of activation.
  • 74
    • 77649209789 scopus 로고    scopus 로고
    • The B3LYP functional, systematically underestimates reaction barrier heights, and is known to be inaccurate for interactions dominated by medium-range correlation energy, such as van der Waals attraction and aromatic-aromatic stacking. See reference [14], and references therein
    • The B3LYP functional, systematically underestimates reaction barrier heights, and is known to be inaccurate for interactions dominated by medium-range correlation energy, such as van der Waals attraction and aromatic-aromatic stacking. See reference [14], and references therein.
  • 76
    • 77649195076 scopus 로고    scopus 로고
    • [I0]
    • [I0]
  • 77
    • 77649211052 scopus 로고    scopus 로고
    • [10] In the light of the present results, this factor, although significant, cannot be considered the dominant one
    • [10] In the light of the present results, this factor, although significant, cannot be considered the dominant one.
  • 78
    • 77649213438 scopus 로고    scopus 로고
    • [10]we erroneously considered evolution of the complex 6-R,anti-S,anti-P (Table 2, entry 10) as the most important catalytic cycle of the heterochiral dimer. Moreover, we did not succeed in locating the TS (6-R,anti-R,syn-P7-R,anti-RS) at the HF/ S3-21Gd level of theory
    • [10]we erroneously considered evolution of the complex 6-R,anti-S,anti-P (Table 2, entry 10) as the most important catalytic cycle of the heterochiral dimer. Moreover, we did not succeed in locating the TS (6-R,anti-R,syn-P7-R,anti-RS) at the HF/ S3-21Gd level of theory.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.