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Volumn 130, Issue 3, 2008, Pages 1003-1011

Polarizing the nazarov cyclization: The impact of dienone substitution pattern on reactivity and selectivity

Author keywords

[No Author keywords available]

Indexed keywords

ACIDS; POLARIZATION; POSITIVE IONS; SUBSTRATES;

EID: 38349106508     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja077162g     Document Type: Article
Times cited : (150)

References (88)
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    • For other recent examples of interrupted Nazarov cyclization, see a
    • For other recent examples of interrupted Nazarov cyclization, see (a) Dhoro, F.; Tius, M. A. J. Am. Chem. Soc. 2005, 127, 12472.
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    • He, W.; Sun, X.; Frontier, A. J. J. Am. Chem. Soc. 2003, 125, 14278-14279; addition/correction J. Am. Chem. Soc. 2004, 126, 10493.
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    • Concurrent to our studies, Flynn and co-workers cyclized similar substrates with a stoichiometric amount of methylsulfonic acid MeSO 3H, see ref 17
    • 3H): see ref 17.
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    • Carbon numbers in Figure 1 were assigned for the purposes of X-ray structure analysis and are not consistent with the numbering scheme used in the rest of the article.
    • Carbon numbers in Figure 1 were assigned for the purposes of X-ray structure analysis and are not consistent with the numbering scheme used in the rest of the article.
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    • C,H coupling constants: see Kingsbury, C. A.; Draney, D.; Sopchik, A.; Rissler, W.; Durham, D. J. Org. Chem. 1976, 41, 3863.
    • C,H coupling constants: see Kingsbury, C. A.; Draney, D.; Sopchik, A.; Rissler, W.; Durham, D. J. Org. Chem. 1976, 41, 3863.
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    • We observed slow reversion of a neat sample of a single isomer (isolated by chromatography) to the thermodynamic mixture in days at 25°C.
    • We observed slow reversion of a neat sample of a single isomer (isolated by chromatography) to the thermodynamic mixture in days at 25°C.
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    • 2.
    • 2.
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    • NOE data were used to assign stereochemistry: see Supporting Information
    • NOE data were used to assign stereochemistry: see Supporting Information.
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    • The poor reactivity of cyclopentenyl-substituted β-ketoester alkylidenes has been documented: see ref 16
    • The poor reactivity of cyclopentenyl-substituted β-ketoester alkylidenes has been documented: see ref 16.
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    • 2 as catalyst. When pure E/Z 20 or 28 was subjected to copper triflate, the interconversion was observed within 5 min of mixing by NMR at rt. The isomers had reached equilibrium before any cyclization took place.
    • 2 as catalyst. When pure E/Z 20 or 28 was subjected to copper triflate, the interconversion was observed within 5 min of mixing by NMR at rt. The isomers had reached equilibrium before any cyclization took place.
  • 69
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    • Ecation is most efficiently delocalized in these substrates, accounting for the facility of the isomerization
    • cation is most efficiently delocalized in these substrates, accounting for the facility of the isomerization.
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    • cation), the process could be viewed as an example of dynamic kinetic diastereoselection.
    • cation), the process could be viewed as an example of dynamic kinetic diastereoselection.
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    • It is likely that a similar process is responsible for the stereoselectivity observed in the rearrangement of furfuryl carbinols to 3-hydroxycyclopentenones: (a) Piancatelli, G, Scettri, A, Barbadoro, S. Tetrahedron Lett. 1976, 17, 3555
    • It is likely that a similar process is responsible for the stereoselectivity observed in the rearrangement of furfuryl carbinols to 3-hydroxycyclopentenones: (a) Piancatelli, G.; Scettri, A.; Barbadoro, S. Tetrahedron Lett. 1976, 17, 3555.
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    • For a theoretical analysis of this reaction with conclusions consistent with our experimental findings, see (b) Faza, O. N, Lopez, C. S, Alvarez, R, de Lera, A. R. Chem. Eur. J. 2004, 10, 4324
    • For a theoretical analysis of this reaction with conclusions consistent with our experimental findings, see (b) Faza, O. N.; Lopez, C. S.; Alvarez, R.; de Lera, A. R. Chem. Eur. J. 2004, 10, 4324.
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    • Experiments conducted with high loadings of catalyst were complicated by poor solubility of the copper(II) salts in chlorinated solvents
    • Experiments conducted with high loadings of catalyst were complicated by poor solubility of the copper(II) salts in chlorinated solvents.
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    • Asymmetric Nazarov cyclization has been accomplished with the use of chiral auxiliaries; see ref 17 and (a) Tius, M. A, Harrington, P. E. Org. Lett. 2000, 2, 2447
    • Asymmetric Nazarov cyclization has been accomplished with the use of chiral auxiliaries; see ref 17 and (a) Tius, M. A.; Harrington, P. E. Org. Lett. 2000, 2, 2447.
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    • For the use of chiral Lewis acids, f see ref 18 and Liang, G, Trauner, D. J. Am. Chem. Soc. 2004, 126, 9544
    • For the use of chiral Lewis acids, (f) see ref 18 and Liang, G.; Trauner, D. J. Am. Chem. Soc. 2004, 126, 9544.
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    • Recently, catalytic asymmetric Nazarov cyclization has been achieved using chiral Bronsted acids: (g) Rueping, M.; Ieawsuwan, W.; Antonchick, A. P.; Nachtsheim, B. J. Angew. Chem., Int. Ed. 2007, 46, 2097.
    • Recently, catalytic asymmetric Nazarov cyclization has been achieved using chiral Bronsted acids: (g) Rueping, M.; Ieawsuwan, W.; Antonchick, A. P.; Nachtsheim, B. J. Angew. Chem., Int. Ed. 2007, 46, 2097.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.