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Volumn 7, Issue 21, 2005, Pages 4673-4676

Oxidative dehydrogenation of dihydropyrimidinones and dihydropyrimidines

Author keywords

[No Author keywords available]

Indexed keywords

CARBONIC ACID DERIVATIVE; COPPER; CUPRIC CHLORIDE; POTASSIUM; POTASSIUM CARBONATE; PYRIMIDINE DERIVATIVE; PYRIMIDINONE DERIVATIVE; TERT BUTYL HYDROPEROXIDE;

EID: 27144451484     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol051879w     Document Type: Article
Times cited : (95)

References (68)
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    • Trost, B. M., Fleming, I., Eds; Pergamon: Oxford, UK
    • (a) Comprehensive Organic Syntheses; Trost, B. M., Fleming, I., Eds; Pergamon: Oxford, UK, 1992; Vol. 7.
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  • 2
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    • Mijs, W. J., De Jonge, C. R. H. I., Eds; Plenium Press: New York
    • (b) Organic Syntheses by Oxidation with Metal Compounds; Mijs, W. J., De Jonge, C. R. H. I., Eds; Plenium Press: New York, 1986.
    • (1986) Organic Syntheses by Oxidation with Metal Compounds
  • 16
    • 27144559421 scopus 로고    scopus 로고
    • note
    • For representative drugs and pharmacologically active compounds, see The Merck Index Online. The structure search with pyrimidine gave 177 hits, including Bleomycin (glycopeptide antibiotics), Buspirone (anxiolytic), Pyrithiobac (herbicide), and Monastrol (Kinesin EG5 inhibitor).
  • 21
    • 27144446114 scopus 로고    scopus 로고
    • Unpublished results
    • Yamamoto, K. Unpublished results.
    • Yamamoto, K.1
  • 24
    • 27144554140 scopus 로고    scopus 로고
    • note
    • 3 oxidation (for substrate 1i) with use of an ARC apparatus (Fauske, Inc) determined it to be thermally unstable within the test conditions. A runaway event occurred with an onset temperature of 40°C, with heat evolution of 157.5 cal/g (adiabatic rise of 205°C) and severe pressure buildup.
  • 25
    • 27144444310 scopus 로고    scopus 로고
    • Jpn. Kokai Tokkyo Koho, 1998, 9 pp; JP 10114755 A2 19980506 Heisei
    • Metal-catalyzed oxidations in related systems: Kuwabe, T.; Okuyama, S.; Hashimoto, S. Jpn. Kokai Tokkyo Koho, 1998, 9 pp; JP 10114755 A2 19980506 Heisei.
    • Kuwabe, T.1    Okuyama, S.2    Hashimoto, S.3
  • 26
    • 27144481551 scopus 로고    scopus 로고
    • note
    • 4, bleach, and molecular oxygen were tested. Only TBHP gave > 10% (by HPLC area) conversion.
  • 27
    • 27144457707 scopus 로고    scopus 로고
    • note
    • 3 in the aqueous phase, which is introduced from the aqueous TBHP solution.
  • 28
    • 27144443324 scopus 로고    scopus 로고
    • note
    • A total of 20 equiv of oxidant was used and the reaction was carried out over an extended period of time.
  • 29
    • 27144550129 scopus 로고    scopus 로고
    • note
    • To eliminate trace amounts of Cu salts introduced from the previous step, the substrate was prepared without a Lewis acid catalyst. See the Supporting Information.
  • 30
    • 27144474892 scopus 로고    scopus 로고
    • note
    • The carbon numbering of dihydropyrimidines and dihydropyrimidinones depends on the substituent pattern. For clarity, the numbering for compound 1a is used for all the substrates in this letter.
  • 31
    • 27144549209 scopus 로고    scopus 로고
    • note
    • 3
  • 32
    • 27144448733 scopus 로고    scopus 로고
    • note
    • 2 catalyst.
  • 39
    • 27144532367 scopus 로고    scopus 로고
    • note
    • 23a the detailed mechanistic investigation was not performed in the present study.
  • 40
    • 0037185537 scopus 로고    scopus 로고
    • and references sited therein
    • (a) Andrus, M. B.; Lashley, J. C. Tetrahedron 2002, 845-866 and references sited therein.
    • (2002) Tetrahedron , pp. 845-866
    • Andrus, M.B.1    Lashley, J.C.2
  • 49
    • 0034008092 scopus 로고    scopus 로고
    • Murahashi, S.-I.; Takaya, H. 2000, 33, 225-233
    • (f) Murahashi, S.-I.; Takaya, H. 2000, 33, 225-233.
  • 51
    • 27144469465 scopus 로고    scopus 로고
    • note
    • 3 are involved in the rate-limiting step (unpublished results).
  • 52
    • 27144498552 scopus 로고    scopus 로고
    • note
    • 2 did not occur (Table 2, entry 12).
  • 54
    • 27144442003 scopus 로고    scopus 로고
    • note
    • 26 but cannot exclude the possibility. We thank one of the reviewers for drawing our attention to this pathway.
  • 56
    • 27144514665 scopus 로고    scopus 로고
    • note
    • As part of our exploratory study, a selection of heterocycles were tested for the dehydrogenation, which further suport the mechanism dipicted in Figure 2. See the Supporting Information.
  • 57
    • 27144510532 scopus 로고    scopus 로고
    • note
    • The structure of peroxide 15d was determined by 2D-NMR (see the Supporting Information).
  • 58
    • 27144475740 scopus 로고    scopus 로고
    • note
    • Preliminary results on isotope effects suggest that the cleavage of the C-H bond at C-6 is involved in the rate-limiting step.
  • 59
    • 27144463935 scopus 로고    scopus 로고
    • note
    • 1/2 ∼ <30 min).
  • 60
    • 27144463934 scopus 로고    scopus 로고
    • note
    • 2/heptane by GC area. The product was collected by filtration and washed with the filtrate (2.0 l), then heptane (1.0 l), and the wet cake was dried under vacuum (∼27-29 Torr) at 40°C. The product 2i (666.1 g, 2.29 mol, 96% yield) was obtained as a white powder, with requisite spectroscopic properties. This procedure has been performed on a ∼ 400 kg (input) scale without incident.
  • 64
    • 18744386111 scopus 로고    scopus 로고
    • Recently, a related oxidation was extended to C-C bond formation. Some representative references: (a) Li, Z.; Li, C.-J. J. Am. Chem. Soc. 2005, 127, 6968-6969.
    • (2005) J. Am. Chem. Soc. , vol.127 , pp. 6968-6969
    • Li, Z.1    Li, C.-J.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.