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more..
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The syn/anti conformations about the C3-C1′ bond were also considered (see the Supporting Information), but their effect on activation energies and product outcome was negligible. See Supporting Information for a complete stereochemical depiction of the reaction course and the computational analysis of the alternative pathways
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The syn/anti conformations about the C3-C1′ bond were also considered (see the Supporting Information), but their effect on activation energies and product outcome was negligible. See Supporting Information for a complete stereochemical depiction of the reaction course and the computational analysis of the alternative pathways.
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73
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Strikingly, this bond reaches 1.79 Å in the stereoisomer that originates from the syn coordination of gold (see Supporting Information) in an almost barrierless process
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Strikingly, this bond reaches 1.79 Å in the stereoisomer that originates from the syn coordination of gold (see Supporting Information) in an almost barrierless process.
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74
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There are authoritative reports in the literature that advocate for a careful use of the term carbene in gold-catalyzed mechanisms and describe these structures as resulting from a p Lewis activation by gold that makes the adjacent carbon more electrophilic, or even a carbocation: a) G. Seidel, R. Mynott, A. Fürstner, Angew. Chem. 2009, 121, 2548-2551;
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76
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b) S. Flügge, A. Anoop, R. Goddard, W. Thiel, A. Fürstner, Chem. Eur. J. 2009, 15, 8558-8565;
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78
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53049098944
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Angew. Chem. Int. Ed. 2008, 47, 5030-5033. The nature of the substituents and the ancillary ligand determine the varying degrees of s and p bonding and the position of the gold species on a continuum from gold-stabilized singlet carbene to gold-stabilized carbocation. See:
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80
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0037419851
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Transition states tsVa and tsVIa are another example of a two-step no-intermediate process using the B3LYP functional; a) D. A. Singleton, C. Hang, M. J. Szymanski, M. P. Meyer, A. G. Leach, K. T. Kuwata, J. S. Chen, A. Greer, C. S. Foote, K. N. Houk, J. Am. Chem. Soc. 2003, 125, 1319-1328;
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b) C. Silva-Lpez, O. Nieto-Faza, R. Alvarez, A. R. de Lera, J. Org. Chem. 2006, 71, 4497-4501. We conducted a relaxed two-dimensional scan[26] starting from Va over the C3-C2′ and C3-C1′ coordinates, corresponding to the bond formation and bond cleavage involved in the indole migration. Figure 1 of the Supporting Information depicts the resulting potential energy surface for the transformation of Va into VIIa in a 3D plot. Although the study discards a concerted transformation, the stepwise process is clearly of low energy (see the Supporting Information).
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P. v. R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao, N. J. R. v. E. Hommes, J. Am. Chem. Soc. 1996, 118, 6317-6318.
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A gold-Nazarov pathway similar to that of VIIa would involve the terminal phenyl group originating from the alternative structure with syn coordination of the gold catalyst to the indole ring. The Supporting Information includes the syn coordination manifold, which is non-competitive with the one shown in Figure 1
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A gold-Nazarov pathway similar to that of VIIa would involve the terminal phenyl group originating from the alternative structure with syn coordination of the gold catalyst to the indole ring. The Supporting Information includes the syn coordination manifold, which is non-competitive with the one shown in Figure 1.
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85
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Prepared from indole 1r by lithiation with nBuLi in THF and further treatment with the corresponding electrophile (diphenyl disulfide and ethyl chloroformate). See the Supporting Information
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Prepared from indole 1r by lithiation with nBuLi in THF and further treatment with the corresponding electrophile (diphenyl disulfide and ethyl chloroformate). See the Supporting Information.
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86
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See ref. [3c]
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See ref. [3c].
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unpublished results. See, also reference [8a] and [8b]
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No more than 1 equiv of starting alkynol should be used for the alkylation step as we have observed that an excess of the propargylic alcohol has a deleterious effect on the gold catalysis
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No more than 1 equiv of starting alkynol should be used for the alkylation step as we have observed that an excess of the propargylic alcohol has a deleterious effect on the gold catalysis.
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