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29944443794
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note
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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).
-
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51
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0029055488
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0027104822
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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.
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57
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29944431535
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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).
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-
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58
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29944446025
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note
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2Me will be addressed later in this paper using perturbation theory.
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59
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84944273288
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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.
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29944447337
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note
-
Strictly speaking, the orbitale are Kohn-Sham orbitals.
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-
-
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63
-
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29944441610
-
-
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
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29944441880
-
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note
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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.
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-
-
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65
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29944447005
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note
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2H, 30, constitutes an exception, being cis, rather that irons, selective. However the degree of selectivity for this molecule is insignificant.
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66
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0041299873
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White, J. D.; Sheldon, B. G.; Solheim, B. A.; Clardy, J. Tetrahedron Lett. 1978, 19, 5189-5192.
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67
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17444414622
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68
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29944442043
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note
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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.
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69
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29944440223
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Manuscript in preparation.
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Pearson, E. L.; Turner, C. I.; Kwan, L. C. H.; Jones, G. A.; Willis, A. C.; Paddon-Row, M. N.; Sherburn, M. S. Manuscript in preparation.
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Pearson, E.L.1
Turner, C.I.2
Kwan, L.C.H.3
Jones, G.A.4
Willis, A.C.5
Paddon-Row, M.N.6
Sherburn, M.S.7
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70
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33845183407
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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.
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(1989)
J. Org. Chem.
, vol.54
, pp. 915-930
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Coe, J.W.1
Roush, W.R.2
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71
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0000048482
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(b) Roush, W. R. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Paquette, L. A., Eds,; Pergamon: Oxford, 1991; Vol. 5, pp 513-550.
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(1991)
Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Paquette, L. A., Eds,; Pergamon: Oxford
, vol.5
, pp. 513-550
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Roush, W.R.1
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72
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17444383126
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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.
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(2005)
Org. Lett.
, vol.7
, pp. 1355-1358
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Dineen, T.A.1
Roush, W.R.2
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73
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note
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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.
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