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Volumn 74, Issue 19, 2009, Pages 7294-7299

Allylic and allenic halide synthesis via NbCl5- and NbBr 5-mediated alkoxide rearrangements

Author keywords

[No Author keywords available]

Indexed keywords

ALKOXIDES; AROMATIC ALCOHOLS; CHEMICAL EQUATIONS; DISPLACEMENT MECHANISMS; NUCLEOPHILIC ADDITIONS;

EID: 70349454069     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo901287f     Document Type: Article
Times cited : (21)

References (126)
  • 2
    • 0004293179 scopus 로고    scopus 로고
    • Kirby, A. J. Oxford University Press: Bath, U.K., Chapter 5
    • Stereoelectronic Effects; Kirby, A. J. Oxford University Press: Bath, U.K., 1998; Chapter 5.
    • (1998) Stereoelectronic Effects
  • 5
    • 36849070454 scopus 로고    scopus 로고
    • For recent applications in synthesis, see: (a)
    • For recent applications in synthesis, see: (a) Smith, A. B., III; Basu, K.; Bosanac, T. J. Am. Chem. Soc. 2007, 129, 14872.
    • (2007) J. Am. Chem. Soc. , vol.129 , pp. 14872
    • Smith III, A.B.1    Basu, K.2    Bosanac, T.3
  • 58
    • 4544320494 scopus 로고    scopus 로고
    • Krause, N., Hashmi, A. S. K., Eds., Wiley: Weinheim, Germany
    • Modern Allene Chemistry, Krause, N., Hashmi, A. S. K., Eds., Wiley: Weinheim, Germany 2004.
    • (2004) Modern Allene Chemistry
  • 59
    • 70349769724 scopus 로고    scopus 로고
    • For the development of "chemically economical" strategies, see
    • For the development of "chemically economical" strategies, see: Burns, N. Z; Baran, P. S; Hoffmann, R. W. Angew. Chem., Int. Ed. 2009, 48, 2854.
    • (2009) Angew. Chem., Int. Ed. , vol.48 , pp. 2854
    • Burns, N.Z.1    Baran, P.S.2    Hoffmann, R.W.3
  • 60
    • 36448991961 scopus 로고    scopus 로고
    • For related metallotropic rearrangements with allylic alcohols, see: a
    • For related metallotropic rearrangements with allylic alcohols, see: a) Fox, R. J.; Lalic, G.; Bergman, R. G. J. Am. Chem. Soc. 2007, 129, 14144.
    • (2007) J. Am. Chem. Soc. , vol.129 , pp. 14144
    • Fox, R.J.1    Lalic, G.2    Bergman, R.G.3
  • 65
    • 70349465588 scopus 로고    scopus 로고
    • For a summary of sigmatropic rearrangements of propargyl-type π-systems to allenic derivatives, see: 2005 and references therein
    • For a summary of sigmatropic rearrangements of propargyl-type π-systems to allenic derivatives, see: Banert, K. Liebigs Ann/Recuil 1997, 2005 and references therein.
    • (1997) Liebigs Ann/Recuil
    • Banert, K.1
  • 73
    • 55749084181 scopus 로고    scopus 로고
    • Refluxing the bromomagnesium alkoxide intermediate does not afford any allylic bromide
    • Bouziane, A.; Carboni, B.; Bruneau, C.; Carreaux, F.; Renaud, J.-L. Tetrahedron 2008, 64, 11745. Refluxing the bromomagnesium alkoxide intermediate does not afford any allylic bromide.
    • (2008) Tetrahedron , vol.64 , pp. 11745
    • Bouziane, A.1    Carboni, B.2    Bruneau, C.3    Carreaux, F.4    Renaud, J.-L.5
  • 74
    • 70349468648 scopus 로고    scopus 로고
    • note
    • A search using SciFinder Scholar identified over 4,000 reactions in which vinylmagnesium bromide affords an allylic alcohol (04/27/09).
  • 75
    • 70349454893 scopus 로고    scopus 로고
    • note
    • A control experiment in which non-1-en-3-ol was treated with vinylmagnesium bromide led only to recovered alcohol, establishing that the bromomagnesium alkoxide does not participate in a bromo-[3,3] rearrangment.
  • 76
    • 70349461829 scopus 로고    scopus 로고
    • note
    • KH was consistently superior over MeMgCl, BuLi, and NaH.
  • 77
    • 0032558912 scopus 로고    scopus 로고
    • For the strong M-O bond energy in the series Ti-O, Zr-O, Nb-O, see: (a)
    • For the strong M-O bond energy in the series Ti-O, Zr-O, Nb-O, see: (a) Loock, H.-P.; Simard, B.; Wallin, S.; Linton, C. J. Chem. Phys. 1998, 109, 8980.
    • (1998) J. Chem. Phys. , vol.109 , pp. 8980
    • Loock, H.-P.1    Simard, B.2    Wallin, S.3    Linton, C.4
  • 82
    • 70349460574 scopus 로고    scopus 로고
    • note
    • Dry niobium pentachloride powder was weighed in a glovebox and transferred directly to the reaction flask under a blanket of dry nitrogen.
  • 83
    • 0034596922 scopus 로고    scopus 로고
    • 5 is expected to be of similar, though unknown, acidity
    • 5 is expected to be of similar, though unknown, acidity: Kobayashi, S.; Busujima, T.; Nagayama, S. Chem.-Eur. J. 2000, 6, 3491.
    • (2000) Chem.-Eur. J. , vol.6 , pp. 3491
    • Kobayashi, S.1    Busujima, T.2    Nagayama, S.3
  • 86
    • 70349458615 scopus 로고    scopus 로고
    • note
    • See ref 10.
  • 91
    • 70349450556 scopus 로고    scopus 로고
    • note
    • The niobium-based chlorination tolerates excess KH.
  • 92
    • 0003965863 scopus 로고
    • Presumably because of the low solvent polarity, which has a dielectric constant of 2.209 at 25 °C: Weast, R. C., Ed.; CRC Press: Boca Raton
    • Presumably because of the low solvent polarity, which has a dielectric constant of 2.209 at 25 °C: CRC Handbook of Chemistry and Physics; Weast, R. C., Ed.; CRC Press: Boca Raton, 1983-1984; E-51.
    • (1983) CRC Handbook of Chemistry and Physics
  • 94
    • 70349463761 scopus 로고    scopus 로고
    • note
    • The authors have deposited the crystallographic data with the Cambridge Crystallographic Data Center (CCDC no. 712587). The data can be obtained, on request, from the Director, Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, U.K.
  • 95
    • 0003549646 scopus 로고    scopus 로고
    • 1H NMR coupling constants of the allylic chloride, nitrile, and sulfide were all 15, which falls in the range for a trans-alkene but is only slightly greater than the normal range for cis-alkenes: Wiley: Chichester
    • 1H NMR coupling constants of the allylic chloride, nitrile, and sulfide were all 15, which falls in the range for a trans-alkene but is only slightly greater than the normal range for cis-alkenes: Gunther, H. In NMR Spectroscopy. Basic Principles, Concepts, and Applications in Chemistry, 2nd ed.; Wiley: Chichester, 1998; p 45.
    • (1998) NMR Spectroscopy. Basic Principles, Concepts, and Applications in Chemistry, 2nd Ed. , pp. 45
    • Gunther, H.1
  • 97
    • 70349458614 scopus 로고    scopus 로고
    • note
    • 5-promoted cyclization, but considerable decomposition occurs, which could potentially cause selective removal of one or more of the allylic chlorides.
  • 98
    • 70349468647 scopus 로고    scopus 로고
    • note
    • 5 affords mainly geranyl bromide (86%) accompanied by terpenyl bromide (12%) consistent with a more rapid cyclization of any linaloyl bromide.
  • 99
    • 35348993725 scopus 로고    scopus 로고
    • 5, in the absence of base, affords only trace amounts of the chloride : (a)
    • 5, in the absence of base, affords only trace amounts of the chloride : (a) Yadav, J. S.; Bhunia, D. C.; Krishna, K. V.; Srihari, P. Tetrahedron Lett. 2007, 48, 8306.
    • (2007) Tetrahedron Lett. , vol.48 , pp. 8306
    • Yadav, J.S.1    Bhunia, D.C.2    Krishna, K.V.3    Srihari, P.4
  • 101
  • 104
    • 49049131900 scopus 로고
    • 5 is required to avoid transmetallation to an organoniobium species because these organoniobiums are weak nucleophiles that do not react with ketones
    • 5 is required to avoid transmetallation to an organoniobium species because these organoniobiums are weak nucleophiles that do not react with ketones: Kauffmann, T.; Antfang, E.; Ennen, B.; Klas, N. Tetrahedron Lett. 1982, 23, 2301.
    • (1982) Tetrahedron Lett. , vol.23 , pp. 2301
    • Kauffmann, T.1    Antfang, E.2    Ennen, B.3    Klas, N.4
  • 105
    • 70349463760 scopus 로고    scopus 로고
    • note
    • 20
  • 106
    • 70349461826 scopus 로고    scopus 로고
    • note
    • Optimization experiments revealed the necessity of THF in the Grignard addition as the use of dioxane caused incomplete addition.
  • 107
    • 70349455550 scopus 로고    scopus 로고
    • note
    • Close scrutiny of the intermediate chloride revealed the presence of less than 5% of a closely related material that was eventually identified as the corresponding (E)-allylic bromide. The naphthyl bromide could arise by in situ displacement of the chloride by the bromide present from the Grignard reagent or potentially through a mixed Mg-Nb species.
  • 108
    • 0037191026 scopus 로고    scopus 로고
    • 4 acts through a direct displacement on the oxygen-bearing carbon
    • 4 acts through a direct displacement on the oxygen-bearing carbon: Shi, M.; Wang, C.-J. Tetrahedron 2002, 58, 9063.
    • (2002) Tetrahedron , vol.58 , pp. 9063
    • Shi, M.1    Wang, C.-J.2
  • 109
    • 70349477309 scopus 로고    scopus 로고
    • note
    • 1H NMR analysis of the crude allylic chloride or bromide indicated complete rearrangement to the allylic halide prior to the sulfenylate displacement.
  • 111
    • 70349471894 scopus 로고    scopus 로고
    • note
    • 1H NMR analysis being consistent with methyl-ether cleavage.
  • 112
    • 70349474769 scopus 로고    scopus 로고
    • note
    • Performing the addition-rearrangement-sulfenylate displacement with piperonal proceeded in 20% yield with the minor reaction components exhibiting spectral data consistent with acetal cleavage.
  • 113
    • 67849091011 scopus 로고    scopus 로고
    • For recent uses of bromoallenes, see: (a)
    • For recent uses of bromoallenes, see: (a) Zhang, W.; Xu, H.; Xu, H.; Tang, W. J. Am. Chem. Soc. 2009, 131, 3832.
    • (2009) J. Am. Chem. Soc. , vol.131 , pp. 3832
    • Zhang, W.1    Xu, H.2    Xu, H.3    Tang, W.4
  • 126
    • 70349455549 scopus 로고    scopus 로고
    • note
    • Thin layer chromatography allows convenient monitoring of sluggish reactions. Samples can be directly removed and applied to a TLC plate and are conveniently analyzed because most allylic alcohols are considerably more polar than the corresponding chloride.


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