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Volumn 46, Issue 6, 2007, Pages 1910-1923

Palladium-catalyzed aerobic oxidative amination of alkenes: Development of intra- and intermolecular aza-Wacker reactions

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; PALLADIUM;

EID: 34047161855     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic061997v     Document Type: Review
Times cited : (286)

References (138)
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    • The term unactivated alkene is subject to a variety of interpretations. In the present context, we use this term to mean simple alkyl olefins, which traditionally have been among the least reactive alkenes in catalytic intermolecular amination reactions. Vinyl ethers, vinylarenes, dienes, and other alkenes containing electron-withdrawing or -donating groups or possessing the ability to chelate a metal center exhibit varying levels of activation. In addition, substrates that undergo intramolecular reaction should not be described as unactivated alkenes because of their intrinsic entropic activation relative to substrates that undergo intermolecular reaction.
    • The term "unactivated alkene" is subject to a variety of interpretations. In the present context, we use this term to mean simple alkyl olefins, which traditionally have been among the least reactive alkenes in catalytic intermolecular amination reactions. Vinyl ethers, vinylarenes, dienes, and other alkenes containing electron-withdrawing or -donating groups or possessing the ability to chelate a metal center exhibit varying levels of "activation". In addition, substrates that undergo intramolecular reaction should not be described as " unactivated" alkenes because of their intrinsic entropic "activation" relative to substrates that undergo intermolecular reaction.
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    • Most of the successful examples have been achieved only recently: (a) Ryu, J.-S.; Li, G. Y.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 12584-12605.
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    • Gas-phase free energies of eqs 1 and 2 were obtained from density functional theory calculations (B3LYP/6-311++G**). Benchmarking studies comparing experimental and calculated energies suggest that the calculated values are within approximately 3 kcal/mol of the experimental data. See: Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Pople, J. A. J. Chem. Phys. 1997, 106, 1063-1079.
    • Gas-phase free energies of eqs 1 and 2 were obtained from density functional theory calculations (B3LYP/6-311++G**). Benchmarking studies comparing experimental and calculated energies suggest that the calculated values are within approximately 3 kcal/mol of the experimental data. See: Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Pople, J. A. J. Chem. Phys. 1997, 106, 1063-1079.
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    • Formation of the Markovnikov enamine product in eq 2 is favored by 36.8 kcal/mol; formation of the imine tautomer is even more favorable, ΔG = -40.7 kcal/mol.
    • Formation of the Markovnikov enamine product in eq 2 is favored by 36.8 kcal/mol; formation of the imine tautomer is even more favorable, ΔG = -40.7 kcal/mol.
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    • For a recent extension of this method for the preparation of (Z)-enamides via palladium-catalyzed oxidative amidation of conjugated olefins, see: Lee, J. M.; Ahn, D.-S.; Jung, D. Y.; Lee, J.; Do, Y.; Kim, S. K.; Chang, S. J. Am. Chem. Soc. 2006, 128, 12954-12962.
    • (b) For a recent extension of this method for the preparation of (Z)-enamides via palladium-catalyzed oxidative amidation of conjugated olefins, see: Lee, J. M.; Ahn, D.-S.; Jung, D. Y.; Lee, J.; Do, Y.; Kim, S. K.; Chang, S. J. Am. Chem. Soc. 2006, 128, 12954-12962.
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    • In general, carbamates are more readily deprotected amine derivatives than sulfonamides, although both have been used widely in organic synthesis. For a general discussion of nitrogen protecting groups, see: Green, T. W, Wuts, P. G. M, Eds, Wiley-VCH: New York
    • In general, carbamates are more readily deprotected amine derivatives than sulfonamides, although both have been used widely in organic synthesis. For a general discussion of nitrogen protecting groups, see: Green, T. W., Wuts, P. G. M., Eds. Protective Groups in Organic Synthesis; Wiley-VCH: New York, 1999.
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    • Note that the palladium species G is not identical under the two reaction conditions. Triethylamine, which leads to the formation of the Markovnikov product, is also a good ligand for palladium, and the alkene complex H forms as a steady-state intermediate. In the absence of triethylamine, however, the kinetics are consistent with pre-equilibrium formation of the alkene complex H. This mechanistic distinction underlies the different [palladium] terms in the rate laws: [LnPd-L, for the Et3N-containing reaction (eq 12a) and [Pd]t in the absence of Et3N eq 13a, For more detailed discussion of the kinetics and rate laws for these reactions, see ref 38 and associated Supporting Information
    • 3N (eq 13a). For more detailed discussion of the kinetics and rate laws for these reactions, see ref 38 and associated Supporting Information.
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    • The alkene insertion step probably proceeds via the initial coordination of the alkene. A first-order dependence on [styrene] will be observed with or without precoordination of the alkene, provided the alkene adduct in the former case does not build up and contribute to the resting state of the catalyst.
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    • A similar catalytic condition had been identified in related reactions involving vinyl transfer to alcohols: (a) Handerson, S.; Schlaf, M. Org. Lett. 2002, 4, 407-409.
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    • Examples of trans-aminopalladation are well documented. For leading references, see: (b) Åkermark, B.; Zetterberg, K. J. Am. Chem. Soc. 1984, 106, 5560-5561.
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    • Analogous reactions were reported for allyl alcohols. See ref 49 and subsequent work by the groups of Morken and Hosokawa (refs 51 and 52, respectively).
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    • For use of PhI(OAc)2 in the palladium-catalyzed intramolecular aminoacetoxylation and diamination of alkenes, see: (a) Alexanian, E. J.; Lee, C.; Sorensen, E. J. J. Am. Chem. Soc. 2005, 127, 7690-7691.
    • For use of PhI(OAc)2 in the palladium-catalyzed intramolecular aminoacetoxylation and diamination of alkenes, see: (a) Alexanian, E. J.; Lee, C.; Sorensen, E. J. J. Am. Chem. Soc. 2005, 127, 7690-7691.
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    • The, recently discovered palladium-catalyzed, dialkoxylation of 2-vinylphenols proceeds by yet another mechanism involving quinone methide intermediates: Schultz, M. J.; Sigman, M. S. J. Am. Chem. Soc. 2006, 128, 1460-1461.
    • (e) The, recently discovered palladium-catalyzed, dialkoxylation of 2-vinylphenols proceeds by yet another mechanism involving quinone methide intermediates: Schultz, M. J.; Sigman, M. S. J. Am. Chem. Soc. 2006, 128, 1460-1461.
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    • For an exception in which osmium-catalyzed aminohydroxylation of styrenes was used to prepare α-arylglycines, see: Reddy, K. L.; Sharpless, K. B. J. Am. Chem. Soc. 1998, 120, 1207-1217.
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    • Both cis- and trans-heteropalladations of alkenes are possible. See refs 28b and 54c, the following examples, and references cited therein: (a) Lei, A.; Lu, X.; Liu, G. Tetrahedron Lett. 2004, 45, 1785-1788.
    • Both cis- and trans-heteropalladations of alkenes are possible. See refs 28b and 54c, the following examples, and references cited therein: (a) Lei, A.; Lu, X.; Liu, G. Tetrahedron Lett. 2004, 45, 1785-1788.
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    • II-C bonds has been observed to proceed with retention or inversion. See ref 46c, the following selected examples, and references cited therein: (a) Coulson, D. R. J. Am. Chem. Soc. 1969, 91, 200-202.
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    • unpublished results
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