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Volumn 121, Issue 18, 1999, Pages 4334-4339

Unexpected complexity in the thermal [(π)2 + (σ)2 + (σ)2] cycloaddition reactions of quadricyclane: Theory and isotope effects

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE; ACETYLENEDICARBOXYLIC ACID DIMETHYL ESTER; ALICYCLIC HYDROCARBON; ALKENE; ALKYNE; BENZENE; DEUTERIUM; DICYANOACETYLENE; ETHYLENE; QUADRICYCLANE; UNCLASSIFIED DRUG;

EID: 0033549042     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983033b     Document Type: Article
Times cited : (21)

References (41)
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    • For reviews of density-functional methods, see: (c) Ziegler, T. Chem. Rev. 1991, 91, 651. (d) Density Functional Methods in Chemistry; Labanowski, J., Andzelm, J., Eds.; Springer: Berlin, 1991. (e) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
    • (1991) Chem. Rev. , vol.91 , pp. 651
    • Ziegler, T.1
  • 12
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    • Springer: Berlin
    • For reviews of density-functional methods, see: (c) Ziegler, T. Chem. Rev. 1991, 91, 651. (d) Density Functional Methods in Chemistry; Labanowski, J., Andzelm, J., Eds.; Springer: Berlin, 1991. (e) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
    • (1991) Density Functional Methods in Chemistry
    • Labanowski, J.1    Andzelm, J.2
  • 13
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    • Oxford University Press: New York
    • For reviews of density-functional methods, see: (c) Ziegler, T. Chem. Rev. 1991, 91, 651. (d) Density Functional Methods in Chemistry; Labanowski, J., Andzelm, J., Eds.; Springer: Berlin, 1991. (e) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
    • (1989) Density-Functional Theory of Atoms and Molecules
    • Parr, R.G.1    Yang, W.2
  • 16
    • 0030018945 scopus 로고    scopus 로고
    • B3LYP/6-31G(d) DFT has proved to give excellent results in comparisons of biradical and concerted mechanisms for pericyclic reactions. See, for example: (a) Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036. (b) Houk, K. N.; Beno, B. R.; Nendel, M.; Black, K.; Yoo, H. Y.; Wilsey, S.; Lee, J. K. J. Mol. Struct. (Theochem) 1997, 398-399, 169.
    • (1996) J. Am. Chem. Soc. , vol.118 , pp. 6036
    • Goldstein, E.1    Beno, B.2    Houk, K.N.3
  • 17
    • 30244518651 scopus 로고    scopus 로고
    • B3LYP/6-31G(d) DFT has proved to give excellent results in comparisons of biradical and concerted mechanisms for pericyclic reactions. See, for example: (a) Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036. (b) Houk, K. N.; Beno, B. R.; Nendel, M.; Black, K.; Yoo, H. Y.; Wilsey, S.; Lee, J. K. J. Mol. Struct. (Theochem) 1997, 398-399, 169.
    • (1997) J. Mol. Struct. (Theochem) , vol.398-399 , pp. 169
    • Houk, K.N.1    Beno, B.R.2    Nendel, M.3    Black, K.4    Yoo, H.Y.5    Wilsey, S.6    Lee, J.K.7
  • 18
    • 0344550040 scopus 로고    scopus 로고
    • note
    • (a) Conformations a, b, and c for the acetylene-quadricyclane system are characterized by the value of the dihedral angle C9-C8-C1-C5: a, ∼0°; b, ∼130°; c, ∼230°. Conformation 4b has a dihedral angle of 159°. Conformation 4c does not exist. (b) Conformations for the ethylene-quadricyclane system are characterized by the dihedral angle C9-C8-C1-C5: a, ∼65°; b, ∼180°; c, ∼315°.
  • 20
    • 0344980987 scopus 로고    scopus 로고
    • note
    • There are two other conformations of 7, namely 7b and 7c, which are able to take the indirect route depicted in Scheme 2. However, the transition structure, 8a, for the direct conversion of 7a into 2 lies, respectively, 3.0 and 4.2 kcal/mol lower in energy than the transition structures for the conversion of 7b and 7c into the respective norbornenyl biradicals 9b and 9c. The direct pathway, proceeding from 7a, is therefore favored. The dihedral angle C9-C8-C1-C5 is 5.8° for 7a, 130° for 7b, and 236° for 7c. See Supporting Information for further details.
  • 21
    • 0345412259 scopus 로고    scopus 로고
    • note
    • 2〉 of the UB3LYP/6-31G(d) wave function for biradical transition structure 4a is 0.1.
  • 22
    • 0344118394 scopus 로고    scopus 로고
    • note
    • Details can be found in the Supporting Information.
  • 25
    • 0344550039 scopus 로고    scopus 로고
    • note
    • D1 is defined (ref 4) as the ratio of product arising from attack of the reagent at C6 and C7 of 18 to that formed from attack at C1 and C5.
  • 26
    • 9344269016 scopus 로고
    • 6 or the program QUIVER (Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989.)
    • (1995) J. Phys. Chem. , vol.99 , pp. 3093
    • Rauhut, G.1    Pulay, P.2
  • 28
    • 0345412258 scopus 로고    scopus 로고
    • note
    • Labeled quadricyclanes were synthesized by photochemical closure of the corresponding labeled norbornadienes, which were in turn prepared by H/D exchange and Shapiro reaction on the corresponding ketones. Details are given in the Supporting Information.
  • 29
    • 0344550037 scopus 로고    scopus 로고
    • note
    • See Table 1 for an explanation of SKIE nomenclature.
  • 36
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    • and references therein
    • See, for example: Kim, E.; Christi, M.; Kochi, J. K. Chem. Ber. 1990, 123, 1209 and references therein.
    • (1990) Chem. Ber. , vol.123 , pp. 1209
    • Kim, E.1    Christi, M.2    Kochi, J.K.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.