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Volumn 11, Issue 16, 2009, Pages 3598-3601

Intramolecular Ir(I)-catalyzed benzylic C-H bond amination of ortho-substituted aryl azides

Author keywords

[No Author keywords available]

Indexed keywords

AZIDE; INDOLE DERIVATIVE; INDOLINE; IRIDIUM;

EID: 68949084911     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol901317j     Document Type: Article
Times cited : (98)

References (53)
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    • Ir-catalysts were found to be significantly less reactive than the corresponding Rh-complexes, see: a
    • Ir-catalysts were found to be significantly less reactive than the corresponding Rh-complexes, see: (a) Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science 2000, 287, 1995.
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    • Reviews of aliphatic C-H bond functionalization: (a) Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507.
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    • For recent, leading reports of related Pd-catalyzed C-H aminations, see:(a) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M. J. Am. Chem. Soc. 2006, 128, 9048.
    • For recent, leading reports of related Pd-catalyzed C-H aminations, see:(a) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M. J. Am. Chem. Soc. 2006, 128, 9048.
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    • Please refer to the Supporting Information for a complete listing of the transition metal complexes examined
    • Please refer to the Supporting Information for a complete listing of the transition metal complexes examined.
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    • When air and water were not rigorously excluded from the reaction mixture, only 10-15% of aniline 5 was produced.
    • When air and water were not rigorously excluded from the reaction mixture, only 10-15% of aniline 5 was produced.
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    • The formation of aniline appears to inhibit the reaction. When 10 mol % of aniline was added to the reaction mixture, no consumption of azide 4 was observed.
    • The formation of aniline appears to inhibit the reaction. When 10 mol % of aniline was added to the reaction mixture, no consumption of azide 4 was observed.
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    • For related reports on the thermolysis or photolysis of aryl azides with alkyl-ortho-substituents, see: (a) Rapoport, H.; Smolinsky, G. J. Am. Chem. Soc. 1960, 82, 934.
    • For related reports on the thermolysis or photolysis of aryl azides with alkyl-ortho-substituents, see: (a) Rapoport, H.; Smolinsky, G. J. Am. Chem. Soc. 1960, 82, 934.
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    • The pyrolysis of ortho-alkyl substituted aryl azides produces indolines in moderate to good yields: For example, 3-methylindoline (44%), 2-ethylindoline (55%), hexahydrocarbazole (86%). See: ref 9b and Smolinsky, G
    • The pyrolysis of ortho-alkyl substituted aryl azides produces indolines in moderate to good yields: for example, 3-methylindoline (44%), 2-ethylindoline (55%), hexahydrocarbazole (86%). See: ref 9b and Smolinsky, G. J. Org. Chem. 1961, 26, 4108.
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    • Irradiation of ortho-alkyl-substituted aryl azides leads to varied yields of indolines: while insertion of the nitrene into a tertiary C-H bond occurs to form 50% of the indoline (see ref 9d, insertion into a secondary C-H bond produces only 11% of the indoline product see ref 9d
    • Irradiation of ortho-alkyl-substituted aryl azides leads to varied yields of indolines: while insertion of the nitrene into a tertiary C-H bond occurs to form 50% of the indoline (see ref 9d), insertion into a secondary C-H bond produces only 11% of the indoline product (see ref 9d).
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    • For recent, leading mechanistic studies of related iridium-mediated C-H bond activations, see: (a) ref 1a and 1b. (b) Yung, C. M.; Skaddan, M. B.; Bergman, R. G. J. Am. Chem. Soc. 2004, 126, 13033.
    • For recent, leading mechanistic studies of related iridium-mediated C-H bond activations, see: (a) ref 1a and 1b. (b) Yung, C. M.; Skaddan, M. B.; Bergman, R. G. J. Am. Chem. Soc. 2004, 126, 13033.
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    • For a discussion of the effect of aryl-substitution on benzylic C-H bond activation, see: a
    • For a discussion of the effect of aryl-substitution on benzylic C-H bond activation, see: (a) Driver, T. G.; Day, M. W.; Labinger, J. A.; Bercaw, J. E. Organometallics 2005, 24, 3644.
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    • For recent reports of Ir-catalyzed C-atom-transfer reactions, see: a
    • For recent reports of Ir-catalyzed C-atom-transfer reactions, see: (a) Lebel, H.; Ladjel, C. Organometallics 2008, 27, 2676.
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    • For the crystal structure of benzyl azide coordinated to an Ir(III)-complex through the R-N-atom, see: Albertin, G.; Antoniutti, S.; Baldan, D.; Castro, J.; Garcia-Fontan, S. Inorg. Chem. 2008, 47, 742.
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    • For a review of the H-atom abstraction-recombination mechanism of the related C-H bond hydroxylation, see: Newcomb, M, Toy, P. H. Acc. Chem. Res. 2000, 33, 449
    • For a review of the H-atom abstraction-recombination mechanism of the related C-H bond hydroxylation, see: Newcomb, M.; Toy, P. H. Acc. Chem. Res. 2000, 33, 449.
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    • An intramolecular KIE of 3.5 was measured for the Rh2II, catalyzed C-H amination reaction of adamantane-1,3-d2. See: Mueller, P, Baud, C, Naegeli, I. J. Phys. Org. Chem. 1998, 11, 597
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    • A mechanism involving the oxidative addition of the C-H bond is possible, but we believe unlikely. Kinetic isotope effects of 2.0 and 4.6 were reported for iridium-catalyzed aryl C-H bond borylation. See: ref 13c.
    • A mechanism involving the oxidative addition of the C-H bond is possible, but we believe unlikely. Kinetic isotope effects of 2.0 and 4.6 were reported for iridium-catalyzed aryl C-H bond borylation. See: ref 13c.
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    • A range of intramolecular kinetic isotope effects (2.8-8.7) were observed in the oxidation of adamantane with PhIdO-metalloporphyrin systems. See: Sorokin, A.; Robert, A.; Meunier, B. J. Am. Chem. Soc. 1993, 115, 7293.
    • A range of intramolecular kinetic isotope effects (2.8-8.7) were observed in the oxidation of adamantane with PhIdO-metalloporphyrin systems. See: Sorokin, A.; Robert, A.; Meunier, B. J. Am. Chem. Soc. 1993, 115, 7293.
  • 53
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    • If indoline is produced by an H-atom abstraction/radical recombination mechanism, it is not apparent why azide 8m does not produce product.
    • If indoline is produced by an H-atom abstraction/radical recombination mechanism, it is not apparent why azide 8m does not produce product.


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