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The striking resemblance of the reactive intermediates of enyne cycloisomerizations to non-classical cations has already been emphasized in the first mechanistic analysis of such transformations, cf;
-
The striking resemblance of the reactive intermediates of enyne cycloisomerizations to "non-classical" cations has already been emphasized in the first mechanistic analysis of such transformations, cf;
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2)] might be more adequately viewed as an iminium cation in the coordination sphere of a gold template, cf. Ref. [4] and literature therein.
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Rapid oligomerization occurred even with catalytic amounts of 4a. The resulting products were complex isomeric mixtures.
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In addition, the more basic phosphines do not undergo ligand exchange on the NMR timescale, as is the case for the PPh3 containing species 5. In some NMR samples of 5, there were no couplings between 31P and the protons or 13C atoms of the organometallic residue. This fact is attributed to a rapid exchange of ligated and free PPh3 in this complex. This exchange could be suppressed by carefully adjusting the stoichiometry of the reactants
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3 in this complex. This exchange could be suppressed by carefully adjusting the stoichiometry of the reactants.
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For formal C-H insertion reactions, see Ref. [11a, b]; for further pertinent examples, see: a H.-S. Yeom, J.-E. Lee, S. Shin, Angew. Chem. 2008, 120, 7148-7151;
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For formal C-H insertion reactions, see Ref. [11a, b]; for further pertinent examples, see: a) H.-S. Yeom, J.-E. Lee, S. Shin, Angew. Chem. 2008, 120, 7148-7151;
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Angew. Chem. Int. Ed. 2008, 47, 7040-7043;
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the metathesis activity of the gold carbene [(IMes)Au=CHPh]′ generated in the mass spectrometer is also worth considering. Strikingly, however, this species effects metathesis only for 1,2-dimethoxyethene, which delivers a Fischer carbene wherein the positive charge is well stabilized by the methoxy substituent; in contrast, regular olefins were found to undergo cyclopropanation, cf. Ref. [9b].
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c) the metathesis activity of the gold carbene [(IMes)Au=CHPh]′ generated in the mass spectrometer is also worth considering. Strikingly, however, this species effects metathesis only for 1,2-dimethoxyethene, which delivers a Fischer carbene wherein the positive charge is well stabilized by the methoxy substituent; in contrast, regular olefins were found to undergo cyclopropanation, cf. Ref. [9b].
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