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Volumn 121, Issue 47, 1999, Pages 10865-10874

Reinvestigation of the isotope effects for the Claisen and aromatic claisen rearrangements: The nature of the Claisen transition states

Author keywords

[No Author keywords available]

Indexed keywords

ETHER DERIVATIVE; ISOTOPE;

EID: 0033486016     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992372h     Document Type: Article
Times cited : (141)

References (65)
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    • See, for example, the discussions in refs 5c and 5d on the relationship of solvent effects to transition state geometry
    • See, for example, the discussions in refs 5c and 5d on the relationship of solvent effects to transition state geometry.
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    • For related studies, see: (a) Houk, K. N.; Gustafson, S. M.; Black, K. A. J. Am. Chem. Soc. 1992, 114, 8565-72. (b) Storer, J. W.; Raimondi, L.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 9675. (c) Wiest, O.; Houk, K. N.; Black, K. A.; Thomas, B., IV. J. Am. Chem. Soc. 1995, 117, 8594.
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    • The calculations used the program QUIVER (Saunders, M.; Laidig, K. E.: Wolfsberg, M. J. Am. Chem. Soc. 1989, III, 8989) with Becke3LYP. RHF, MP2, and AMI frequencies scaled by 0.9614,0.91,0.943, and 0.953, respectively. (Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502). CASSCF and MP4(SDQ) scaling factors of 0.9015 and 0.951, respectively, were based on a least-squares fit with the scaled Becke3LYP frequencies for the starting allyl vinyl ether.
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    • The calculations used the program QUIVER (Saunders, M.; Laidig, K. E.: Wolfsberg, M. J. Am. Chem. Soc. 1989, III, 8989) with Becke3LYP. RHF, MP2, and AMI frequencies scaled by 0.9614,0.91,0.943, and 0.953, respectively. (Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502). CASSCF and MP4(SDQ) scaling factors of 0.9015 and 0.951, respectively, were based on a least-squares fit with the scaled Becke3LYP frequencies for the starting allyl vinyl ether.
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    • note
    • trans positions, respectively, which are within experimental error of the values found for allyl phenyl ether.
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    • This method was developed by S. R. Merrigan in this laboratory
    • This method was developed by S. R. Merrigan in this laboratory.
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    • note
    • 1.9 - 1 = 1.2% when expected values for the old KIEs are calculated from the new.
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