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Volumn 6, Issue 17, 2004, Pages 3013-3015

Platinum(II)-catalyzed 1,6-diene cycloisomerizations: Turnover in the absence of β-hydride elimination

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; CATION; CYCLOHEXENE DERIVATIVE; CYCLOPROPANE DERIVATIVE; LIGAND; PLATINUM DERIVATIVE;

EID: 4444239138     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol048780u     Document Type: Article
Times cited : (66)

References (42)
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    • and references therein
    • See ref 2 and also: (a) Johnson, W. S.; Bartlett, W. R.; Czeskis, B. A.; Gautier, A.; Lee, C. H.; Lemoine, R.; Leopold, E. J.; Luedtke, G. R.; Bancroft, K. J. J. Org. Chem. 1999, 64, 9587 and references therein, (b) Ishihara, K.; Ishibashi, H.; Yamamoto, H. J. Am. Chem. Soc. 2002, 124, 3647. (c) Nishizawa, M.; Takenaka, H.; Hayashi, Y. J. Org. Chem. 1986, 51, 806. (d) Corey, E. J.; Wood, H. B. J. Am. Chem. Soc. 1996, 118, 11982 and references therein.
    • (1999) J. Org. Chem. , vol.64 , pp. 9587
    • Johnson, W.S.1    Bartlett, W.R.2    Czeskis, B.A.3    Gautier, A.4    Lee, C.H.5    Lemoine, R.6    Leopold, E.J.7    Luedtke, G.R.8    Bancroft, K.J.9
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    • See ref 2 and also: (a) Johnson, W. S.; Bartlett, W. R.; Czeskis, B. A.; Gautier, A.; Lee, C. H.; Lemoine, R.; Leopold, E. J.; Luedtke, G. R.; Bancroft, K. J. J. Org. Chem. 1999, 64, 9587 and references therein, (b) Ishihara, K.; Ishibashi, H.; Yamamoto, H. J. Am. Chem. Soc. 2002, 124, 3647. (c) Nishizawa, M.; Takenaka, H.; Hayashi, Y. J. Org. Chem. 1986, 51, 806. (d) Corey, E. J.; Wood, H. B. J. Am. Chem. Soc. 1996, 118, 11982 and references therein.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 3647
    • Ishihara, K.1    Ishibashi, H.2    Yamamoto, H.3
  • 8
    • 33845376064 scopus 로고
    • See ref 2 and also: (a) Johnson, W. S.; Bartlett, W. R.; Czeskis, B. A.; Gautier, A.; Lee, C. H.; Lemoine, R.; Leopold, E. J.; Luedtke, G. R.; Bancroft, K. J. J. Org. Chem. 1999, 64, 9587 and references therein, (b) Ishihara, K.; Ishibashi, H.; Yamamoto, H. J. Am. Chem. Soc. 2002, 124, 3647. (c) Nishizawa, M.; Takenaka, H.; Hayashi, Y. J. Org. Chem. 1986, 51, 806. (d) Corey, E. J.; Wood, H. B. J. Am. Chem. Soc. 1996, 118, 11982 and references therein.
    • (1986) J. Org. Chem. , vol.51 , pp. 806
    • Nishizawa, M.1    Takenaka, H.2    Hayashi, Y.3
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    • and references therein
    • See ref 2 and also: (a) Johnson, W. S.; Bartlett, W. R.; Czeskis, B. A.; Gautier, A.; Lee, C. H.; Lemoine, R.; Leopold, E. J.; Luedtke, G. R.; Bancroft, K. J. J. Org. Chem. 1999, 64, 9587 and references therein, (b) Ishihara, K.; Ishibashi, H.; Yamamoto, H. J. Am. Chem. Soc. 2002, 124, 3647. (c) Nishizawa, M.; Takenaka, H.; Hayashi, Y. J. Org. Chem. 1986, 51, 806. (d) Corey, E. J.; Wood, H. B. J. Am. Chem. Soc. 1996, 118, 11982 and references therein.
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    • Corey, E.J.1    Wood, H.B.2
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  • 16
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    • Diene cycloisomerization processes do not typically give cyclopropanes; see: (a) Lloyd-Jones, G. C. Org. Biomol. Chem. 2003, 1, 215. (b) Widenhoefer, R. A. Acc. Chem. Res. 2002, 35, 905.
    • (2003) Org. Biomol. Chem. , vol.1 , pp. 215
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  • 17
    • 0036798179 scopus 로고    scopus 로고
    • Diene cycloisomerization processes do not typically give cyclopropanes; see: (a) Lloyd-Jones, G. C. Org. Biomol. Chem. 2003, 1, 215. (b) Widenhoefer, R. A. Acc. Chem. Res. 2002, 35, 905.
    • (2002) Acc. Chem. Res. , vol.35 , pp. 905
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    • Ene-ynes, on the other hand, do typically give cyclopropanes: (c) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317.
    • (2004) Chem. Rev. , vol.104 , pp. 1317
    • Diver, S.T.1    Giessert, A.J.2
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    • note
    • This nomenclature first refers to the bond being activated and then the nucleophilic bond.
  • 22
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    • Cation-olefin cyclizations with oxonium initiators also proceed selectively via this conformer; see ref 2a and: (a) Seiders, J. R., II; Wang, L.; Floreancig, P. E. J. Am. Chem. Soc. 2003, 125, 2406. (b) Johnson, W. S.; van der Gen, A.; Swoboda, J. J. J. Am. Chem. Soc. 1967, 89, 170.
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    • Seiders II, J.R.1    Wang, L.2    Floreancig, P.E.3
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    • Cation-olefin cyclizations with oxonium initiators also proceed selectively via this conformer; see ref 2a and: (a) Seiders, J. R., II; Wang, L.; Floreancig, P. E. J. Am. Chem. Soc. 2003, 125, 2406. (b) Johnson, W. S.; van der Gen, A.; Swoboda, J. J. J. Am. Chem. Soc. 1967, 89, 170.
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    • Johnson, W.S.1    Van Der Gen, A.2    Swoboda, J.J.3
  • 33
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    • note
    • Friedel-Craft-type cyclization on the activated ortho positions is intuitively reasonable, though we have no proof at this time.
  • 35
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    • For recent examples, see: (a) Nagumo, S.; Ono, M.; Kakimoto, Y.; Furukawa, T.; Hisano. T.; Mizukami, M.; Kawahara, N.; Akita, H. J. Org. Chem. 2002, 67, 6618. (b) Nagumo, S.; Ishii, Y.; Kakimoto, Y.; Kawahara, N. Tetrahedron Lett. 2002, 43, 5333.
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  • 38
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    • Alternative 1,4- or 1,5-transfers from the ring are also possible, (a) Saunders: M.; Jimenez-Vazquez, H. A. Chem. Rev. 1991, 91, 375. (b) Watt, C. I. F. In Advances in Physical Organic Chemistry, Bethell, D., Ed.; Academic Press: New York, 1988; Vol. 24, p 57.
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  • 39
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    • Bethell, D., Ed.; Academic Press: New York
    • Alternative 1,4- or 1,5-transfers from the ring are also possible, (a) Saunders: M.; Jimenez-Vazquez, H. A. Chem. Rev. 1991, 91, 375. (b) Watt, C. I. F. In Advances in Physical Organic Chemistry, Bethell, D., Ed.; Academic Press: New York, 1988; Vol. 24, p 57.
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  • 40
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    • note
    • Control experiments showed that 1b catalyzes the isomerization of 4,4-dimethylcyclohexene to 3,3-dimethylcyclohexene.
  • 41
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    • note
    • Pt catalysts 1a and 1b are completely selective for 3 and 5, respectively. No traces of cyclohexenes were detected (GC) in the crude cyclopropane reaction mixtures, and vice versa.


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