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34547510627
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The existence of gold carbenoid vs. cationic intermediates is still a matter of debate, see:
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15
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33748792796
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For recent reviews on cyclopropenes, see:
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S. López E. Herrero-Gómez P. Pérez-Galán C. Nieto-Oberhuber A. M. Echavarren Angew. Chem., Int. Ed. 2006 45 6029
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Echavarren, A.M.5
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19
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46049088039
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and references cited therein When the reaction was repeated at a higher temperature of 60°C in DCE, the selectivity plummeted (1:1 of 2g:3g). Indeed, all the reactions shown in Table 1 should be run at ≤20°C to ensure good selectivities
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Z. Zhang R. A. Widenhoefer Org. Lett. 2008 10 2079
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20
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25444522675
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Formation of tert-allylic alcohol from 3,3-dimethylcyclopropene-1,2- dicarboxylate and water is known with Pd(0), albeit in low selectivity. See:
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N. Mézailles L. Richard F. Gagosz Org. Lett. 2005 7 4133
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G. Lemiére V. Gandom N. Agenet J. -P. Goddard A. de Kozak C. Aubert L. Fensterbank M. Malacria Angew. Chem., Int. Ed. 2006 45 7596
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29
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35048842179
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DFT studies on a related gold vinyl carbenoid species have shown that the C1-C2 and C2-C3 bonds are almost equally long, suggesting that the positive charge is highly delocalized in π orbitals of the conjugated system involving the Au, C1, C2 and C3 atoms; see:
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C. H. M. Amijs V. López-Carrillo A. M. Echavarren Org. Lett. 2007 9 4021
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38349014690
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Similar rearrangements have been reported with rhodium(ii) catalysts, although with much lower yields. See:
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A. Correa N. Marion L. Fensterbank M. Malacria S. P. Nolan L. Cavallo Angew. Chem., Int. Ed. 2008 47 718
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84987344424
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Pd catalysed indene formation from related cyclopropenes have been proposed to occur via π-allylic complexes, see:
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P. Müller C. Granicher Helv. Chim. Acta 1995 78 129
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