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32744468380
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note
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Co(0)-catalyzed expansion of 1-alkynylcyclopropanols affords cyclopentenones and, in some cases, small amounts of the alkylidenecyclobutanone:
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For an excellent review of homogeneous gold-catalyzed reactions, see: Hashmi, A. S. K. Gold Bull. 2004, 37, 51.
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Hashmi, A.S.K.1
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32744455305
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For reviews of Ag(I)-catalyzed rearrangement of strained oσ-bonds, see: (a) Paquette, L. A. Acc. Chem. Res. 1971, 4, 281.
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0009679346
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(b) Bishop, K. C., III. Chem. Rev. 1976, 76, 461. For Au-catalyzed rearrangement of small ring hydrocarbons, see:
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Bishop III, K.C.1
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32744458723
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3/AgOTf 4%, HBr 0%. See also: Wasserman, R. E.; Cochoy, R. E.; Baird, M. S. J. Am. Chem. Soc. 1969, 91, 2376.
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32744454922
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note
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Under identical reaction conditions. Au(I)-catalyzed reaction of non-terminal alkynylcyclobutanols produced complex mixtures.
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28
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22144432396
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For stoichioraetric formation of triphenylphosphinegold(I)-homoenolates from cyclopropanols, see: Murakami, M.; Inouve, M.; Suginome, M.; Ito, Y. Bull. Chem. Soc. Jpn. 1988, 61, 3649. In accord with this report, we found that 3 catalyzed the rearrangement of vinylcyclopropanol 42 to ketone 43. (Diagram presented)
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Murakami, M.1
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29
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0033599513
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A related mechanism has been proposed for formation of methylidene cyclopentanones by Pd(II)-catalyzed rearrangement of a vinylcyclobutanols. See: Nishimura, T.; Ohe, K.; Uemura, S. J. Am. Chem. Soc. 1999, 121, 2645.
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32744457556
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note
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Consistent with the kinetic formation of (E)-alkenes, olefin geometry in cyclobutanone 44 is not isomerized under the reaction conditions. (Diagram presented)
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For an example of reversal of migratory aptitude in ring expansion due to inductive effects, see: Trost, B. M.; Ornstein, P. L. J. Ori>. Chem. 1985, 48, 1133.
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For recent approaches to highly substituted cyclopentanones from vinyl cyclopropanes, see: (a) Navseschuk, C. G.; Rovis, T. Angew. Chem., Int. Ed. 2005, 44, 3264.
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(b) Davies, H. M. L.; Xiang, B.; Kong, N.; Stafford, D. G. J. Am, Chem. Soc. 2001, 123, 7461.
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