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Juaristi, E., Ed.; VCH Publishers: New York and Weinheim, ch. 5
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note
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In any case, each calculation must be carefully considered individually. One should note that restricted Hartree-Fock (RHF) calculations on transition states where the nucleophile is a small anion (e.g., hydride) are suspect because the probable single electron transfer from the anion to the ketone cannot be treated by this method. See section III.B.1 for more detailed discussion.
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4
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0346678221
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note
-
Figure 2 is drawn with the orbital splittings approximately of equal magnitude for the symmetrical and unsymmetrical orbital interactions. This is strictly true only for the approximation where S (overlap) = 0.
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0346047580
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note
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One should note that the ΔHreaction of the reduction product depends on the nucleophile. Thus, the selectivity for attack by methide (for example) should differ from that of hydride.
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36
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Baker, J. W. Hyperconjugation; Oxford University Press: London, 1952.
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Baker, J.W.1
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Huet, J.; Maroni-Barnaud, Y.; Anh, N. T.; Seyden-Penne, J. Tetrahedron Lett. 1976, 159.
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Eisenstein, O.; Klein, J.; Lefour, J. M. Tetrahedron 1979, 35, 225.
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33748232180
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For a criticism of this analysis, see Wu, Y. D.; Houk, K. N.; Paddon-Row, M. N. Angew. Chem., Int. Ed. Engl. 1992, 31, 1019-21
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An earlier paper by Paddon-Row and Houk et al. reported calculations (HF/STO-3G) on propene with a fixed hydride, proton, or H-atom 2 Å above the olefinic plane, in what may be the earliest report of this type. (J. Am. Chem. Soc. 1981, 103, 2438-40). We used this methodology for formaldehyde plus a hydride. This yielded charge transfers of 0.81, 0.54, and 0.22 at 1.4, 2.0, and 8.0 Å, respectively, above the C=O.
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0346678199
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note
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Some of the compounds have oxygens as part of both substituents at the 4-position.
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