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Ni-catalyzed reactions with organoboron reagents: (a) Patel, S. J.; Jamison, T. F. Angew. Chem., Int. Ed. 2003, 42, 1364. Iridium-catalyzed processes with hydrogen incorporation:
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Selected examples of gold-catalyzed intermolecular annulations: (a) Melhado, A. D.; Luparia, M.; Toste, F. D. J. Am. Chem. Soc. 2007, 129, 12638.
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Recent work on propargyl tosylates: (a) Schwier, T.; Sromek, A. W.; Yap, D. M. L.; Chernyak, D.; Gevorgyan, V. J. Am. Chem. Soc. 2007, 129, 9868. Revisions on the reactivity of propargyl esters:
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Overall view on NHC in synthesis: (a) N-Heterocyclic Carbenes in Synthesis;Nolan, S. P., Ed.; Wiley-VCH: Weinheim, Germany, 2006. Recent work on determination of stereoelectronic parameters associated with NHC ligands, see:
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Overall view on NHC in synthesis: (a) N-Heterocyclic Carbenes in Synthesis;Nolan, S. P., Ed.; Wiley-VCH: Weinheim, Germany, 2006. Recent work on determination of stereoelectronic parameters associated with NHC ligands, see:
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Improved gold-catalyzed reactions are realized when switching from PPh3 to the NHC IPr ligand; see, for instance: (a) Marion, N.; Díez- González, S.; de Frémont, P.; Noble, A. R.; Nolan, S. P. Angew. Chem. Int. Ed. 2006, 45, 3647.
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Improved gold-catalyzed reactions are realized when switching from PPh3 to the NHC IPr ligand; see, for instance: (a) Marion, N.; Díez- González, S.; de Frémont, P.; Noble, A. R.; Nolan, S. P. Angew. Chem. Int. Ed. 2006, 45, 3647.
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The consumption of the propargyl tosylate was noticed for all of the reactions depicted in Tables 2 and 3, with the exception of 5c 21% of 4a was recovered; extended reaction times did not improve the yield, As a rule, NMR inspection of the reaction crude revealed conversion of starting materials into the corresponding product 5 as the only noticeable major reaction path. The standard column chromatographic purification process was difficult, and partial hydrolysis of compounds 5 occurs to give the related ketone easily, as noticed previously in the obtention of related unsaturated imines; see: Boger, D. L, Corbett, W. L. J. Org. Chem. 1992, 57, 4777. This fact accounts for the moderate isolated yields obtained for some of the unsaturated imines reported
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The consumption of the propargyl tosylate was noticed for all of the reactions depicted in Tables 2 and 3, with the exception of 5c (21% of 4a was recovered; extended reaction times did not improve the yield). As a rule, NMR inspection of the reaction crude revealed conversion of starting materials into the corresponding product 5 as the only noticeable major reaction path. The standard column chromatographic purification process was difficult, and partial hydrolysis of compounds 5 occurs to give the related ketone easily, as noticed previously in the obtention of related unsaturated imines; see: Boger, D. L.; Corbett, W. L. J. Org. Chem. 1992, 57, 4777. This fact accounts for the moderate isolated yields obtained for some of the unsaturated imines reported.
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64349098821
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To date, under the standard conditions, primary substituents at that position fail to yield a clean transformation producing related cycles
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To date, under the standard conditions, primary substituents at that position fail to yield a clean transformation producing related cycles.
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46
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For related intramolecular gold-catalyzed diene formation, see: a
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For 1, 2-alkyl migration in π-acid catalyzed reactions: (a) Crone, B.; Kirsch, S. F. Chem.-Eur. J. 2008, 14, 3514. For ligand effects on migration of propargyl esters, see:
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The rearrangement shows the chemoselectivity of [1, 2]-shifts with or without the occurrence of electron sextets. Bruckner, R. AdVanced Organic Chemistry; Hartcourt/Academic: San Diego, 2002; pp 438-466.
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NMR monitoring of the reaction showed a deshielding of the imine proton upon mixing equimolecular amounts of the reagents providing evidence for the formation of an imine-gold complex. A gold III, catalyzed addition of arenes to imines has been reported in Luo, Y, Li, C.-J. Chem. Commun. 2004, 1930. An alternative pathway involving straightforward addition of the C-Au ff-bond in the complex with the diene-prior to its protonation-cannot be rigorously ruled out at present
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NMR monitoring of the reaction showed a deshielding of the imine proton upon mixing equimolecular amounts of the reagents providing evidence for the formation of an imine-gold complex. A gold (III) -catalyzed addition of arenes to imines has been reported in Luo, Y.; Li, C.-J. Chem. Commun. 2004, 1930. An alternative pathway involving straightforward addition of the C-Au ff-bond in the complex with the diene-prior to its protonation-cannot be rigorously ruled out at present.
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One of the reviewers suggested that the formation of the azetine is a high energy pathway and proposed a plausible alternative that involves the elimination of TsNH2 to form a pentadienone with Ts attached to the carbonyl oxygen and further exchange of TsOH by TsNH2
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2.
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A carbonyl metathesis followed by a Nazarov cyclization has been invoked in: (a) Jin, T.; Yamamoto, Y. Org. Lett. 2008, 10, 3137. For alkyne carbonyl metathesis, see:
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