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Volumn 29, Issue 4, 2010, Pages 1004-1011

Quantum-chemical study of neutral lewis base catalyzed allylation of aldehydes with allyltrichlorosilanes

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION BARRIERS; ALLYL GROUPS; ALLYLATION REACTIONS; ALLYLATIONS; BOND FORMATION; ELECTRON-ACCEPTING; ELECTRON-DONATING ABILITY; LEWIS ACIDITY; LEWIS BASE; MP2/6-31G; N ,N-DIMETHYLFORMAMIDE; NEUTRAL LEWIS BASIS; ORBITAL ANALYSIS; PENTA-COORDINATED STRUCTURE; REPULSIVE INTERACTIONS; SI-C BOND; SILICON CENTERS; TRANSITION STATE; TRIAMIDES;

EID: 76849102439     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om901086q     Document Type: Article
Times cited : (15)

References (84)
  • 5
    • 10044241080 scopus 로고    scopus 로고
    • Yamamoto, H., Oshima, K., Eds. Wiley-VCH: Weinheim, Germany
    • Miura, K.; Hosomi, A. In Main Group Metals in Organic Synthesis; Yamamoto, H., Oshima, K., Eds. Wiley-VCH: Weinheim, Germany, 2004; Vol.2, p 409.
    • (2004) Main Group Metals in Organic Synthesis , vol.2 , pp. 409
    • Miura, K.1    Hosomi, A.2
  • 49
    • 0013325926 scopus 로고
    • For the enhanced reactivity of pentacoordinated anionic silicon species, see: Deiters, J. A.; Holmes, R. R. J. Am. Chem. Soc 1990, 112, 7197-7202.
    • (1990) J. Am. Chem. Soc , vol.112 , pp. 7197-7202
    • Deiters, J.A.1    Holmes, R.R.2
  • 50
    • 76849109360 scopus 로고    scopus 로고
    • note
    • 32d
  • 59
    • 76849107746 scopus 로고    scopus 로고
    • The distance between the silicon and the oxygen in DMF has been calculated to be 3187 Å at the MP2/6-31+G level of theory
    • The distance between the silicon and the oxygen in DMF has been calculated to be 3187 Å at the MP2/6-31+G level of theory.
  • 60
    • 0035144310 scopus 로고    scopus 로고
    • Theoretical studies indicated that the destabilization energy governs the stability of the donor-acceptor complexes of silanes. See: (a) Fleisher, H. Eur. J. Inorg. Chem. 2001, 393-404.
    • (2001) Eur. J. Inorg. Chem. , pp. 393-404
    • Fleisher, H.1
  • 62
    • 76849100742 scopus 로고    scopus 로고
    • note
    • In the case of formaldehyde, there appears another transition state between TS2 and R2 in which the aldehyde molecule has a strongly pyramidized structure. It may not be essential to the allylation reaction. See the Supporting Information.
  • 63
    • 76849104841 scopus 로고    scopus 로고
    • Estimated by the energy difference between TS3 and (the DMFcoordinated allylsilane + benzaldehyde) frozen to the structures in TS3
    • Estimated by the energy difference between TS3 and (the DMFcoordinated allylsilane + benzaldehyde) frozen to the structures in TS3.
  • 64
    • 76849092400 scopus 로고    scopus 로고
    • The energy difference between TS3 and (the benzaldehydecoordinated allylsilane + DMF)
    • The energy difference between TS3 and (the benzaldehydecoordinated allylsilane + DMF).
  • 67
    • 38149037245 scopus 로고    scopus 로고
    • Recently, Denmark et al. carried out synthesis and characterization of the solution and solid-state structures of HMPA adducts of silicon tetrachloride. See: Denmark, S. E.; Eklov, B. M. Chem. Eur. J. 2008, 14, 234-239.
    • (2008) Chem. Eur. J. , vol.14 , pp. 234-239
    • Denmark, S.E.1    Eklov, B.M.2
  • 68
    • 65349192848 scopus 로고    scopus 로고
    • The experimental and theoretical study performed by Hrdina et al. indicated that the allylation reaction of aldehydes catalyzed by bipyridine N, N'-dioxides proceeds via two different reaction mechanisms depending on the solvent. See: Hrdina, R.; Opekar, F.; Roithová, J.; Kotora, M. Chem. Commun. 2009, 2314-2316.
    • (2009) Chem. Commun. , pp. 2314-2316
    • Hrdina, R.1    Opekar, F.2    Roithová, J.3    Kotora, M.4
  • 71
    • 11644266970 scopus 로고
    • 1841-1846, 2338-2342,2343-2346
    • Mulliken, R. S. J. Chem. Phys. 1955, 23,1833-1840,1841-1846, 2338-2342,2343-2346.
    • (1955) J. Chem. Phys. , vol.23 , pp. 1833-1840
    • Mulliken, R.S.1
  • 72
    • 76849116652 scopus 로고    scopus 로고
    • note
    • The bonding contribution of the s-type orbitais in electron derealization is counterbalanced by their antibonding participation in the overlap repulsion between the occupied MOs of the two fragments, and therefore, the s-type orbital functions of Si do not participate in the Si-O(benzaldehyde) bond both at TS1 and at TS3.
  • 78
    • 76849093999 scopus 로고    scopus 로고
    • note
    • a bond not only in TS1 but also in TS3.
  • 79
    • 76849115052 scopus 로고    scopus 로고
    • 1 on the Si center has been found to be 79%, the same magnitude as that in TS3
    • 1 on the Si center has been found to be 79%, the same magnitude as that in TS3.
  • 84
    • 76849101103 scopus 로고    scopus 로고
    • note
    • nonel is the sum of the cavitation, dispersion, and repulsion energies in the SCRF calculations. The united atom, topological model applied to radii optimized at the RHF/6-31G level of theory (UAHF) was utilized for the PCM calculations.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.