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2 (1 atm, balloon), 25 °C) resulted in no reaction.
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The absolute stereochemistry was determined by comparison of the optical rotation with that reported for (-)-2, by Uozumi and Hayashi, ref 12c (see Supporting Information for rotation data). We report the absolute stereochemistry of (+)-8, (-)-6, (+)-4, and (-)-10 by analogy to this substrate.
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For experimental evidence of insertion of tetrafluoroethylene into a Pt-O bond, see: Bryndza, H. E. Organometallics 1985, 4, 406-408.
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2 will form π-allyl complexes by C-H activation of olefins in acetone: Trost, B. M.; Metzner, P. J. J. Am. Chem. Soc. 1980, 102, 3572-3577.
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29344449537
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note
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See Supporting Information for details.
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99
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0037771626
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Examples of anti β-hydrogen elimination under various conditions have been reported, hut involve aromatization or the formation of highly conjugated systems. See: (a) Toyota, M.; Ilangovan, A.; Okamoto, R.; Masaki, T.; Arakawa, M.; Ihara, M. Org. Lett. 2002, 4, 4293-4296.
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103
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0037162732
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For a study that attempts to differentiate between oxypalladation and a π-allyl route for a Pd(II)-catalyzed cyclization. see: Zanoni, G.; Porta, A.; Meriggi, A.; Franzini, M.; Vidari, G. J. Org. Chem. 2002, 67, 6064-6069.
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104
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29344459481
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note
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After 5.5 h, 89% yield of a 1:0.75 mixture of 54 and cis-2-d-55 was obtained.
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106
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29344475811
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note
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2 into the [Pd]-H bond, if turnover of the catalyst occurs by that mechanism. At this time, we cannot rule out any of or distinguish among these possibilities.
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107
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note
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Because both [Pd]-D and [Pd]-H are formed, reinsertion after [Pd] dissociates from product 54 would lead to scrambling of the isotopic label.
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109
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0034828614
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(a) Stahl, S. S.; Thorman, J. L.; Nelson, R. C.; Kozee, M. A. J. Am. Chem. Soc. 2001, 123, 7188-7189.
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2. For recent articles invoking Pd(IV) in Pd-catalyzed oxidative processes, see: (a) Dick, A. R.; Hull, K. L.; Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 2300-2301.
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(e) For a related Pd-catalyzed iodination system, see: Giri, R.; Chen, X.; Yu, J.-Q. Angew. Chem., Int. Ed. 2005, 44, 2112-2115.
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117
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note
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2 and all other reagents except the substrate for 15 min before addition of the substrate.
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118
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29344463449
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note
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The identity of the aldehyde was confirmed by oxidation of the alcohol by another method; see Supporting Information.
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119
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29344463708
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note
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We cannot rule out the possibility that the reaction with dipyridyl as ligand proceeds through similar intermediates with slow, partial dissociation of one of the dipyridyl nitrogen atoms. The reaction with (-)-sparteine as ligand is much less likely to undergo partial dissociation due to its structural rigidity.
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