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2 and Au(III) catalysts can also generate (through different mechanisms) related bicyclopropane structures. See, for example: (a) Harrak, Y.; Blaszykowski, C.; Bernard, M.; Cariou, K.; Mainetti, E.; Mouries, V.; Dhimane, A.-L.; Fensterbank, L.; Malacria, M. J. Am. Chem. Soc. 2004, 126, 8656.
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3242741475
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28
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note
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The balance of material in these reactions is usually alkene-containing isomers that appear to originate from the consumption of cyclopropane.
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23044495830
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note
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31P NMR.
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30
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23044443003
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note
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This nomenclature refers to the position of the electrophilic alkene in the C-C bond-forming transition state.
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31
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4444225192
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Both 6-exo- and 6-endocyclization modes were observed in stoichiometric cascade cyclization of polyenes. See: Koh, J. H.; Gagné, M. R. Angew. Chem., Int. Ed. 2004, 43, 3459-3461.
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Koh, J.H.1
Gagné, M.R.2
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For catalytic asymmetric alkoxycyclization of enynes with Pt(II) and Au(I), see: (a) Charruault, L.; Véronique, M.; Taras, R.; Gladiali, S.; Genêt, J.-P. Chem. Commun. 2004, 851.
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(b) Muñoz, M. P.; Adrio, J.; Carretero, J. C.; Echavarren, A. M. Organometallics 2005, 24, 1293.
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note
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The balance of the material was two Pt-alkyls that remain uncharacterized.
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36
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note
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A single diastereomer was obtained from reductive cleavage of 13b. Although trans relative stereochemistry seems most likely, this has not been conclusively determined.
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37
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note
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A similar OBn abstraction likely mediates the isomerization of 10 to O-Bn geraniol/nerol (entry 5, Table 1).
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0013649939
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48
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see ref 2b
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An alternative possibility is direct metalation to form a Pt(IV) metallacyclobutane followed by reductive elimination. Evidence disfavoring this mechanism includes the observation of cyclopropane products with related Pd(II) catalysts, which would implicate the involvement of a Pd(IV) intermediate; see ref 2b. However, this possibility has not been rigorously disproven.
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