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Volumn 127, Issue 44, 2005, Pages 15391-15393

Oxaziridine-mediated catalytic hydroxylation of unactivated 3° C-H bonds using hydrogen peroxide

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN PEROXIDE; OXAZIRIDINE DERIVATIVE;

EID: 27644563193     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja055549i     Document Type: Article
Times cited : (161)

References (50)
  • 1
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    • Goldberg, K. I., Goldman, A. S., Eds.; ACS Symposium Series 885; American Chemical Society: Washington, DC
    • (a) Goldman, A. S.; Goldberg, K. I. In Activation and Functionalization of C-H Bonds; Goldberg, K. I., Goldman, A. S., Eds.; ACS Symposium Series 885; American Chemical Society: Washington, DC, 2004; pp 1-43.
    • (2004) Activation and Functionalization of C-H Bonds , pp. 1-43
    • Goldman, A.S.1    Goldberg, K.I.2
  • 11
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    • N-Sulfonyloxaziridines have been reported to epoxidize alkenes at elevated temperature. See: Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123-3126.
    • (1983) J. Am. Chem. Soc. , vol.105 , pp. 3123-3126
    • Davis, F.A.1    Harakal, M.E.2    Awad, S.B.3
  • 12
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    • For a comprehensive review on nonmetal-based homogeneous oxidation catalysis, see: Adam, W.; Saha-Möller, C. R.; Ganeshpure, P. A. Chem Rev. 2001, 101, 3499-3548.
    • (2001) Chem Rev. , vol.101 , pp. 3499-3548
    • Adam, W.1    Saha-Möller, C.R.2    Ganeshpure, P.A.3
  • 13
    • 33845280836 scopus 로고
    • For an example of imine-catalyzed sulfide oxidation, see: Davis, F. A.; Lal, S. G. J. Org. Chem. 1988, 53, 5004-5007.
    • (1988) J. Org. Chem. , vol.53 , pp. 5004-5007
    • Davis, F.A.1    Lal, S.G.2
  • 22
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    • Similar effects of fluorination on dioxirane reactivity have been noted. For some leading references, see: (a) Mello, R.; Fiorentino, M.; Fusco, C.; Curci, R. J. Am. Chem. Soc. 1989, 111, 6749-6757.
    • (1989) J. Am. Chem. Soc. , vol.111 , pp. 6749-6757
    • Mello, R.1    Fiorentino, M.2    Fusco, C.3    Curci, R.4
  • 26
    • 15744375697 scopus 로고    scopus 로고
    • Gaussian, Inc.: Wallingford, CT
    • Calculations performed using: Frisch, M. J. et al. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
    • (2004) Gaussian 03, Revision C.02
    • Frisch, M.J.1
  • 27
    • 27644472079 scopus 로고    scopus 로고
    • note
    • Activation energies were calculated relative to isolated reactants.
  • 36
    • 27644555002 scopus 로고    scopus 로고
    • note
    • DMDO is included in the Supporting Information.
  • 37
    • 0000845829 scopus 로고    scopus 로고
    • 1 led to a decrease in energy by 2.3 kcal/mol. A lowering of energy by 1.9 kcal/mol was noted for methane oxidation by dioxirane: see ref 16. Also see: (a) Du, X.; Houk, K. N. J. Org. Chem. 1998, 63, 6480-6483.
    • (1998) J. Org. Chem. , vol.63 , pp. 6480-6483
    • Du, X.1    Houk, K.N.2
  • 39
    • 27644546123 scopus 로고    scopus 로고
    • note
    • The reaction of oxaziridine 3 and 1-decene or adamantane affords the oxidized products with reaction times and product conversions comparable to that of 5. Difficulties associated with the chromatographic separation of the benzoxathiazine byproduct from the desired compounds in addition to the high cost of the starting 2-bromophenol caused us to favor the use of benzoxathiazine 4 for all subsequent experiments.
  • 40
    • 27644536507 scopus 로고    scopus 로고
    • note
    • 1,3-Adamantanediol was produced in small quantities (∼5%) along with trace levels of 2-adamantanone. The absence of halogenated products suggests that freely diffusing radical species are not formed.
  • 44
    • 27644533113 scopus 로고    scopus 로고
    • note
    • 2 and UHP gave <10% conversion to epoxide.
  • 45
    • 27644537843 scopus 로고    scopus 로고
    • note
    • Attempts to oxidize benzylic substrates afforded mixtures of products presumably due to aromatic functionalization.
  • 46
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    • Trans-decalin affords ∼15% yield of trans-9-decalinol with no isomerization to the cis product detected by GC. DMDO oxidizes trans-decalin to trans-9-decalinol in 20% yield. See: Murray, R. W.; Jeyaraman, R.; Mohan, L. J. Am. Chem. Soc. 1986, 108, 2470-2472.
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 2470-2472
    • Murray, R.W.1    Jeyaraman, R.2    Mohan, L.3
  • 47
    • 27644542568 scopus 로고    scopus 로고
    • note
    • 1H NMR. Under the same catalytic conditions, isoamyl benzoate showed 5% conversion to the hydroxylated product after 24 h. Collectively, these data suggest that the selectivity observed in the hydroxylation of dihydrocitronellol benzoate is principally determined by electronic effects.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.