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Volumn 12, Issue 4, 2010, Pages 684-687

Chemoselectivity of the Ru-catalyzed cycloisomerization reaction for the synthesis of dihydropyrans; application to the synthesis of L-forosamine

Author keywords

[No Author keywords available]

Indexed keywords

FOROSAMINE; HEXOSAMINE; PYRAN DERIVATIVE; RUTHENIUM;

EID: 76849117022     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol9026667     Document Type: Article
Times cited : (34)

References (41)
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    • For studies that were published during the preparation of our manuscript, see
    • (e) Trost, B. M. Rhee, Y. H. J. Am. Chem. Soc. 2002, 124, 2528. For studies that were published during the preparation of our manuscript, see:
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 2528
    • Trost, B.M.1    Rhee, H.Y.2
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    • Although not presented in the same study, refs 1c and 2a overlap in demonstration of this compatibility
    • (b) Although not presented in the same study, refs 1c and 2a overlap in demonstration of this compatibility.
  • 13
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    • Intermolecular selectivity (for the carboxylic OH) has been reported in the case of N-carbamate protected amino acids: Doucet, H.; MartinVaca, B.; Bruneau, C.; Dixneuf, P. H. J. Org. Chem. 1995, 60, 7247.
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    • Doucet, H.1    Martinvaca, B.2    Bruneau, C.3    Dixneuf, P.H.4
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    • The known natural products incorporating these 2,3,6-trideoxy- 4dimethylamino glycosides (such, as the spiramycins, spinosyns, ossamycin and dunaimycin D2S) bear β linkages to a macrocyclic core
    • The known natural products incorporating these 2,3,6-trideoxy- 4dimethylamino glycosides (such, as the spiramycins, spinosyns, ossamycin and dunaimycin D2S) bear β linkages to a macrocyclic core.
  • 20
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    • equatorial selectivity is expected in the coupling of an alcohol moiety
    • Chloronitration of a dihydropyran. demonstrated a high equatorial selectivity for the Cl atom. As the mechanism is considered to be stepwise (see Rasmussen, J. K.; Hassner, A. J. Org. Chem. 1974, 39, 2558) equatorial selectivity is expected in the coupling of an alcohol moiety.
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    • By contrast, imidate and glycosyl bromide derivatives of these sugars give predominantly a coupling products. For example, (a) Evans, D. A.; Black, W. C J. Am. Chem. Soc. 1993, 115, 4497.
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    • The analytical yield was 95% based on HPLC assay of the crude reaction mixture. The lower isolated yield is associated with the volatility of 4
    • The analytical yield was 95% based on HPLC assay of the crude reaction mixture. The lower isolated yield is associated with the volatility of 4.
  • 26
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    • 1H NMR. This product was obtained in ∼25% yield as part of a complex reaction mixture
    • 1H NMR. This product was obtained in ∼25% yield as part of a complex reaction mixture.
  • 27
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    • The preferential formation of an N-Boc-pyrroline in related systems (i.e., tungesten vinylidenes in refs 1c, 13) suggests that factors other than product ring size contribute to the observed rate difference
    • The preferential formation of an N-Boc-pyrroline in related systems (i.e., tungesten vinylidenes in refs 1c, 13) suggests that factors other than product ring size contribute to the observed rate difference.
  • 28
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    • See Supporting Information
    • Prepared as a racemate by reduction of Weinreb amide 2 followed by the addition of Me2CuLi according to the procedure of Reetz Reetz, M. F.; Rolfing, K.; Griebenow, N. Tetrahedron Lett. 1994, 35, 1969. See Supporting Information.
    • (1994) Tetrahedron Lett. , vol.35 , pp. 1969
    • Reetz, M.F.1    Rolfing, K.2    Griebenow, N.3
  • 29
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    • Alternatively the reaction may proceed through, a higher energy boat-like transition state that minimizes steric repulsions
    • Alternatively the reaction may proceed through, a higher energy boat-like transition state that minimizes steric repulsions.
  • 30
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    • Such as alkyne dimerization, which was observed without sufficient ligand in the related rhodium catalyzed cycloisomerization. (ref 1d). For a recent example of dimerization using a closely related ruthenium catalyst, see: Daniels, M.; Kirss, R. U. J. Organomet. Chem. 2007, 692, 1716.
    • (2007) J. Organomet. Chem. , vol.692 , pp. 1716
    • Daniels, M.1    Kirss, R.U.2
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    • 3 ligand prior to nucleophilic attack by oxygen. For relevant discussions see reference 1e and Trost, B. M.; Kulawiec, R. J. J. Am. Chem. Soc. 1992, 114, 5579.
    • (1992) Am. Chem. Soc. , vol.114 , pp. 5579
    • Trost, B.M.1    Kulawiec, R.J.J.2
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    • US patent US600 1981, 1999
    • (b) US patent US600 1981, 1999.
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    • US patent US541 2081. 1995
    • (c) US patent US541 2081. 1995.
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    • Eur. Pat. Appl. EP457215, 1991
    • (d) Eur. Pat. Appl. EP457215, 1991.
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    • Purchased from Acros Organics
    • Purchased from Acros Organics.
  • 37
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    • Determined by chiral HPLC analysis. See Supporting Information
    • Determined by chiral HPLC analysis. See Supporting Information.
  • 38
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    • Although the conversion of 14 to 16 appeared to be efficient, the extraction of 16 into organic solvents was difficult. Upon concentration of the aqueous phase in order to improve the extraction efficiency, glycal 16 was observed to partially dehydrate back to the volatile 15
    • Although the conversion of 14 to 16 appeared to be efficient, the extraction of 16 into organic solvents was difficult. Upon concentration of the aqueous phase in order to improve the extraction efficiency, glycal 16 was observed to partially dehydrate back to the volatile 15.
  • 39
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    • For a sample of previous syntheses, see
    • For a recent synthesis of forosamine, see: (a) Tietze, L. F.; Bönke, N.; Dietz, S. Org. Lett. 2009, 11, 2948. For a sample of previous syntheses, see:
    • (2009) Org. Lett. , vol.11 , pp. 2948
    • Tietze, L.F.1    Bönke, N.2    Dietz, S.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.