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Volumn 28, Issue 8, 2009, Pages 2583-2594

A theoretical study of nickel(0)-Catalyzed phenylcyanation of alkynes. Reaction mechanism and regioselectivity

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVE SPECIES; ALKYNE INSERTIONS; FORMATION PROCESS; OXIDATIVE ADDITIONS; RATE DETERMINING STEP; REACTION MECHANISM; REDUCTIVE ELIMINATION; STERIC REPULSIONS; THEORETICAL STUDY; VINYL GROUP;

EID: 65749099443     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om8008525     Document Type: Article
Times cited : (60)

References (51)
  • 29
    • 65749119640 scopus 로고    scopus 로고
    • We tried to perform the IRC calculation, but it failed in several cases here probably because of too flat of a potential energy surface. We ascertained that each transition state connects reactant and product on the potential energy surface by performing steepest descent geometry optimization starting from each transition state.
    • note We tried to perform the IRC calculation, but it failed in several cases here probably because of too flat of a potential energy surface. We ascertained that each transition state connects reactant and product on the potential energy surface by performing steepest descent geometry optimization starting from each transition state.
  • 37
    • 65749115306 scopus 로고    scopus 로고
    • sol is neither Gibbs free energy nor Helmholtz free energy because it is the PCM-calculated free energy. Apparently, the PCM- calculated free energy is different from neither Gibbs free energy nor Helmholtz free energy, but it is called free energy because it involves the work necessary to build up solute in continuum solvent.
    • sol is neither Gibbs free energy nor Helmholtz free energy because it is the PCM-calculated free energy. Apparently, the PCM- calculated free energy is different from neither Gibbs free energy nor Helmholtz free energy, but it is called free energy because it involves the work necessary to build up solute in continuum solvent.
  • 40
    • 0038626673 scopus 로고    scopus 로고
    • revision D.02; Gaussian, Inc.: Walling-ford, CT
    • Pople, J. A.; Gaussian 03, revision D.02; Gaussian, Inc.: Walling-ford, CT, 2004.
    • (2004) Gaussian 03
    • Pople, J.A.1
  • 42
    • 65749108727 scopus 로고    scopus 로고
    • evr.
    • evr.
  • 43
    • 65749114692 scopus 로고    scopus 로고
    • ev are 3.6 and 12.2 kcal/mol, respectively) in the PhCN coordination from 2 to 3. These results suggest that the cod dissociation is difficult before PhCN approaches the Ni center
    • ev are 3.6 and 12.2 kcal/mol, respectively) in the PhCN coordination from 2 to 3. These results suggest that the cod dissociation is difficult before PhCN approaches the Ni center
  • 45
    • 65749097285 scopus 로고    scopus 로고
    • 6-7 connects 6 and 7. The IRC calculation did not work because of the very flat potential energy surface around these transition states. See Supporting Information Figure S3 for the geometry and energy changes
    • 6-7 connects 6 and 7. The IRC calculation did not work because of the very flat potential energy surface around these transition states. See Supporting Information Figure S3 for the geometry and energy changes
  • 46
    • 65749096516 scopus 로고    scopus 로고
    • See Supporting Information section S2 in page S-13 for a more detailed discussion.
    • See Supporting Information section S2 in page S-13 for a more detailed discussion.
  • 47
    • 65749092743 scopus 로고    scopus 로고
    • 3 substitution for alkyne.
    • 3 substitution for alkyne.
  • 49
    • 65749095231 scopus 로고    scopus 로고
    • The Ni-CN and Ni-Ph bond energies in 9A were calculated to be 121.8 and 99.1 kcal/mol, respectively. See Supporting Information section S3 in page S-17 for more details of these values.
    • The Ni-CN and Ni-Ph bond energies in 9A were calculated to be 121.8 and 99.1 kcal/mol, respectively. See Supporting Information section S3 in page S-17 for more details of these values.
  • 50
    • 65749103640 scopus 로고    scopus 로고
    • See Supporting Information section S4 in page S-17 for a more detailed discussion.
    • See Supporting Information section S4 in page S-17 for a more detailed discussion.
  • 51
    • 65749115307 scopus 로고    scopus 로고
    • Because 9Aa-R and 9Ab-R easily convert to each other, the concentration ratio [9Aa-R]/[9Ab-R] should be considered to evaluate the regioselectivity.
    • Because 9Aa-R and 9Ab-R easily convert to each other, the concentration ratio [9Aa-R]/[9Ab-R] should be considered to evaluate the regioselectivity.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.