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Volumn 3, Issue 1, 2001, Pages 37-40

Entropy-controlled asymmetric synthesis. How differential activation entropy is induced in chiral tethered reactions

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ARTICLE;

EID: 0001773523     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol006741m     Document Type: Article
Times cited : (36)

References (35)
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    • Sugimura, T.; Yamada, H.; Inoue, S.; Tai, A. Tetrahedron: Assymmetry 1997, 8, 649-655. Sugimura, T.; Inoue, S.; Tai, A. Tetrahedron Lett. 1998, 39, 6487-6490.
    • (1998) Tetrahedron Lett. , vol.39 , pp. 6487-6490
    • Sugimura, T.1    Inoue, S.2    Tai, A.3
  • 12
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    • 3)
    • 3).
  • 13
    • 0042459667 scopus 로고    scopus 로고
    • Structures of the minor products were not identified in all reactions. Values of the de of the major products were determined by GLC with achiral and chiral columns after treatments of the reaction mixtures with lithium aluminum hydride and acetic anhydride/pyridine. Reference samples were prepared through epimerization of the isolated major products followed by the above conversion. The selectivities shown in Table 1 might be underestimated because of intermolecular reactions. See the Supporting Information for the experimental details
    • Structures of the minor products were not identified in all reactions. Values of the de of the major products were determined by GLC with achiral and chiral columns after treatments of the reaction mixtures with lithium aluminum hydride and acetic anhydride/pyridine. Reference samples were prepared through epimerization of the isolated major products followed by the above conversion. The selectivities shown in Table 1 might be underestimated because of intermolecular reactions. See the Supporting Information for the experimental details.
  • 14
    • 18444417883 scopus 로고
    • For reviews, see the following: (a) Doyle, M. P. Chem. Rev. 1986, 86, 919-939.
    • (1986) Chem. Rev. , vol.86 , pp. 919-939
    • Doyle, M.P.1
  • 15
    • 0000769223 scopus 로고
    • Trost, B. M. Ed.; Pergamon Press: Oxford
    • (b) Davis, H. M. In Comprehensive Organic Synthesis; Trost, B. M. Ed.; Pergamon Press: Oxford, 1991; pp 1031-1067.
    • (1991) Comprehensive Organic Synthesis , pp. 1031-1067
    • Davis, H.M.1
  • 17
    • 0026632575 scopus 로고
    • For the intramolecular reactions, see the following: (a) Padwa, A.; Krumpe, K. E. Tetrahedron 1992, 48, 5385-5453.
    • (1992) Tetrahedron , vol.48 , pp. 5385-5453
    • Padwa, A.1    Krumpe, K.E.2
  • 22
    • 0002723024 scopus 로고    scopus 로고
    • Padwa, A.; Austin, D. J.; Price, A. T.; Semones, M. A.; Doyle, M. P.; Protopopova, M. N.; Winchester, W. R.; Tran, A. J. Am. Chem. Soc. 1993, 115, 8669-8680. Padwa, A.; Austin, D. J.; Hornbuckle, S. F. J. Org. Chem. 1996, 61, 63-72.
    • (1996) J. Org. Chem. , vol.61 , pp. 63-72
    • Padwa, A.1    Austin, D.J.2    Hornbuckle, S.F.3
  • 23
    • 0041457714 scopus 로고    scopus 로고
    • The reactivity ratio of isopropoxybenzene and benzene was independently determined from the reaction with ethyl diazoacetate (9.3 ± 0.9)
    • The reactivity ratio of isopropoxybenzene and benzene was independently determined from the reaction with ethyl diazoacetate (9.3 ± 0.9).
  • 24
    • 0004105856 scopus 로고
    • Longman Scientific & Technical: Essex
    • (a) Issacs, N. Physical Organic Chemistry; Longman Scientific & Technical: Essex, 1995; pp 643-677.
    • (1995) Physical Organic Chemistry , pp. 643-677
    • Issacs, N.1
  • 26
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    • Gold, V., Bethell, D., Eds.; Academic Press: London
    • Entropy-driving acceleration of the intramolecular reaction by the methyl substitution is known as the Thorpe-Ingold effect. See the following: (a) Kirby, A. J. In Advances in Physical Organic Chemistry; Gold, V., Bethell, D., Eds.; Academic Press: London, 1980; Vol. 17, pp 183-278.
    • (1980) Advances in Physical Organic Chemistry , vol.17 , pp. 183-278
    • Kirby, A.J.1
  • 30
    • 0001594721 scopus 로고    scopus 로고
    • R - δΔS‡S, respectively. When the chiral perturbation mechanism is similar among the reactions, δΔS ‡ and δΔH‡ show the isokinetic relation, and thus those differences, ΔΔH‡ and ΔΔS‡, should have a linear relationship. For the recent experimental examples, see the following: (a) Gallicchio, E.; Kubo, M. M.; Lecy, R. M. J. Am. Chem. Soc. 1998, 120, 4526-4527.
    • (1998) J. Am. Chem. Soc. , vol.120 , pp. 4526-4527
    • Gallicchio, E.1    Kubo, M.M.2    Lecy, R.M.3
  • 32
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    • A similar explanation for the reaction rate using "critical distance" in nonstereoselective reactions was also reported. Menger, F. M. Acc. Chem. Res. 1985, 18, 128-134.
    • (1985) Acc. Chem. Res. , vol.18 , pp. 128-134
    • Menger, F.M.1


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