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Volumn 70, Issue 26, 2005, Pages 10841-10853

On the origin of cis/trans stereoselectivity in intramolecular Diels-Alder reactions of substituted pentadienyl acrylates: A comprehensive density functional study

Author keywords

[No Author keywords available]

Indexed keywords

ACRYLICS; ISOMERS; OLEFINS; REACTION KINETICS; SUBSTITUTION REACTIONS;

EID: 29944440674     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo051973q     Document Type: Article
Times cited : (27)

References (73)
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    • For other examples of this anomalous trans-selectivity of Z-dienophiles in IMDA reactions, see: (a) White, J. D.; Sheldon, B. G. J. Org. Chem. 1981, 46, 2273-2280.
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    • (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652. For reviews of density-functional methods, see:
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  • 37
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    • Labanowski, J. K., Andzelm, J. W., Eds.; Springer-Verlag: New York
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    • (1991) Density Functional Methods in Chemistry
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    • Schleyer, P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaefer, H. F., III; Schreiner, P. R., Eds.; John Wiley & Sons, Ltd.: Chichester
    • (b) The Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaefer, H. F., III; Schreiner, P. R., Eds.; John Wiley & Sons, Ltd.: Chichester, 1998.
    • (1998) The Encyclopedia of Computational Chemistry
  • 49
    • 29944443794 scopus 로고    scopus 로고
    • note
    • For example, the anti conformation of acetic acid is 25 kJ/mol less stable than the syn conformation (B3LYP/6-31G(d)//HF/3-21G). The anti conformation can be preferred in the presence by external H-bonding acceptors (see later).
  • 51
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    • For IMDA reactions on trienes containing vinylborane dienophiles, see: (a) Singleton, D. A.; Lee, Y.-K. Tetrahedron Lett. 1995, 36, 3473-3476.
    • (1995) Tetrahedron Lett. , vol.36 , pp. 3473-3476
    • Singleton, D.A.1    Lee, Y.-K.2
  • 56
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    • Calculations suggest that the observed endo selectivity for the DA reaction between dienes and acrylonitrile in solution is due to solvent effects: Karcher, T.; Sicking, W.; Sauer, J.; Sustmann, R. Tetrahedron Lett. 1992, 33, 8027-8030.
    • (1992) Tetrahedron Lett. , vol.33 , pp. 8027-8030
    • Karcher, T.1    Sicking, W.2    Sauer, J.3    Sustmann, R.4
  • 57
    • 29944431535 scopus 로고    scopus 로고
    • note
    • The B3LYP/6-31G(d) HOMO/LUMO energies (eV) are: s-trans-butadiene (-6.24/-0.57); but-2-en-1-yne (-6.57/-0.675); acrylonitrile (-7.96/-1.39); nitroethene (-7.86/-2.42); methyl acrylate (-11.1.1/0.001); methyl vinyl ketone (-6.74/-1.64); acrolein (-7.01/-1.84).
  • 58
    • 29944446025 scopus 로고    scopus 로고
    • note
    • 2Me will be addressed later in this paper using perturbation theory.
  • 59
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    • For a related treatment, applied to Lewis acid catalysis of Diels-Alder reactions, see: Houk, K. N.; Strozier, R. W. J. Am. Chem. Soc. 1973, 95, 4094-4096.
    • (1973) J. Am. Chem. Soc. , vol.95 , pp. 4094-4096
    • Houk, K.N.1    Strozier, R.W.2
  • 62
    • 29944447337 scopus 로고    scopus 로고
    • note
    • Strictly speaking, the orbitale are Kohn-Sham orbitals.
  • 63
    • 29944441610 scopus 로고    scopus 로고
    • note
    • Using a stronger electron withdrawing substituent will also polarize the dienophile LUMO towards the substituent, thereby increasing the magnitude of the numerator of eq 1 and further strengthening the SOI term.
  • 64
    • 29944441880 scopus 로고    scopus 로고
    • note
    • Consideration of the LUMO coefficients of other atoms which might give rise to SOIs, such as the carbonyl oxygen atom of the ester and formyl groups, leads to the same conclusions that are derived from considering only the bullet-labeled atoms.
  • 65
    • 29944447005 scopus 로고    scopus 로고
    • note
    • 2H, 30, constitutes an exception, being cis, rather that irons, selective. However the degree of selectivity for this molecule is insignificant.
  • 68
    • 29944442043 scopus 로고    scopus 로고
    • note
    • The predicted endo selectivity for the reaction between s-trans-anti-acrylic acid and butadiene, da32 (Table 2), in contrast to the exo selectivity predicted for the remaining conformations of acrylic acid, da29-da31, arises from stabilizing OH⋯diene-π electrostatic interactions in endo-da32TS; in this TS, the carboxyl group is significantly twisted, by 28°, out of the plane of the dienophile double bond, in the direction of the diene, bringing the OH hydrogen atom fairly close to both C2 and C3 atoms of the diene (ca. 2.7 Å). This effect is absent in cis-Z-32TS; in this TS, the OH forms a hydrogen bond with the tether carbonyl group, with the result that the OH bond is twisted 12° below the plane of the dienophile double bond, away from the diene.
  • 70
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    • Important experimental observations and detailed analyses of transition states of closely related decatrienone systems have reported by Roush and co-workers: (a) Coe, J. W.; Roush, W. R. J. Org. Chem. 1989, 54, 915-930.
    • (1989) J. Org. Chem. , vol.54 , pp. 915-930
    • Coe, J.W.1    Roush, W.R.2
  • 72
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    • Dineen, T. A.; Roush, W. R. Org. Lett. 2005, 7, 1355-1358. For an analysis of hexadienyl acrylate IMDA TSs, see refile.
    • (2005) Org. Lett. , vol.7 , pp. 1355-1358
    • Dineen, T.A.1    Roush, W.R.2
  • 73
    • 29944435632 scopus 로고    scopus 로고
    • note
    • The favored conformation of the forming six membered lactone ring in cis-Z-35TS has the tether carbonyl group nearly coplanar with the dienophile double bond. Coplanarity between tether carbonyl and dienophile cannot take place in the pentadienyl acrylate TSs, even in the absence of a 9-Z-substituent.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.