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Volumn 74, Issue 15, 2009, Pages 5545-5552

Anionic halocuprate(II) complexes as catalysts for the oxaziridine-mediated aminohydroxylation of olefins

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVE CATALYST; AMINOHYDROXYLATION; ANIONIC ADDITIVES; CATALYTICALLY ACTIVE SPECIES; CHEMICAL EQUATIONS; HALIDE ADDITIVES; MODIFIED MECHANISM; OXAZIRIDINES; OXIDATIVE TRANSFORMATIONS; OXIDIZING ABILITY; RADICAL TRAPPING; TERMINAL OXIDANTS;

EID: 68049086802     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo900902k     Document Type: Article
Times cited : (74)

References (49)
  • 11
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    • Halocuprate(I) compounds, on the other hand, are used synthetically and have been shown to be convenient sources of nucleophilic chloride. See: (a) Muscio, O. J. Jr.; Jun, Y. M.; Philip, J. B. Jr. Tetrahedron Lett. 1978, 19, 2379-2382.
    • Halocuprate(I) compounds, on the other hand, are used synthetically and have been shown to be convenient sources of nucleophilic chloride. See: (a) Muscio, O. J. Jr.; Jun, Y. M.; Philip, J. B. Jr. Tetrahedron Lett. 1978, 19, 2379-2382.
  • 16
  • 27
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    • The direct formation of metal-NHC complexes from the reaction of imidazolium salts with metal complexes bearing basic ligands is well-precedented: Herrmann, W. A, Elison, M, Fischer, J, Köcher, C, Artus, G. R. J. Angew. Chem, Int. Ed. Engl. 1995, 34, 2371-2374
    • The direct formation of metal-NHC complexes from the reaction of imidazolium salts with metal complexes bearing basic ligands is well-precedented: Herrmann, W. A.; Elison, M.; Fischer, J.; Köcher, C.; Artus, G. R. J. Angew. Chem., Int. Ed. Engl. 1995, 34, 2371-2374.
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    • (a) Jeffery, T. Tetrahedron 1996, 52, 10113-10130.
    • (1996) Tetrahedron , vol.52 , pp. 10113-10130
    • Jeffery, T.1
  • 33
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    • Radical rearrangements of N-alkyloxaziridines initiated upon oneelectron reduction by copper(I) catalysts have been studied in detail by Aubé. See: (a) Aube, J.; Ghosh, S.; Tanol, M. J. Am. Chem. Soc. 1994, 116, 9009-9018.
    • Radical rearrangements of N-alkyloxaziridines initiated upon oneelectron reduction by copper(I) catalysts have been studied in detail by Aubé. See: (a) Aube, J.; Ghosh, S.; Tanol, M. J. Am. Chem. Soc. 1994, 116, 9009-9018.
  • 35
    • 0037034854 scopus 로고    scopus 로고
    • An intramolecular aminohydroxylation of olefins using N-benzoyloxyamines catalyzed by copper(I) salts has been reported: Noack, M, Göttlich, R. Chem. Commun. 2002, 536-537
    • An intramolecular aminohydroxylation of olefins using N-benzoyloxyamines catalyzed by copper(I) salts has been reported: Noack, M.; Göttlich, R. Chem. Commun. 2002, 536-537.
  • 36
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    • These stoichiometric studies were conducted using copper(I) and copper(II) triflate because of the limited solubility of the chloride and TFA salts in methylene chloride
    • These stoichiometric studies were conducted using copper(I) and copper(II) triflate because of the limited solubility of the chloride and TFA salts in methylene chloride.
  • 37
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    • This mechanism would be similar to the molecule-induced homolysis pathway proposed by Minisci to explain dioxirane-mediated epoxidations: Bravo, A, Fontana, F, Fronza, G, Minisci, F, Zhao, L. J. Org. Chem. 1998, 63, 254-263
    • This mechanism would be similar to the "molecule-induced homolysis" pathway proposed by Minisci to explain dioxirane-mediated epoxidations: Bravo, A.; Fontana, F.; Fronza, G.; Minisci, F.; Zhao, L. J. Org. Chem. 1998, 63, 254-263.
  • 39
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    • Margerum's studies on copper(II) - peptide complexes indicate that multiple anionic ligands facilitate electrochemical oxidation of the metal by stabilizing the copper(III) oxidation state: Bossu, F. P.; Chellappa, K. L.; Margerum, D. W. J. Am. Chem. Soc. 1977, 99, 2195-2203.
    • Margerum's studies on copper(II) - peptide complexes indicate that multiple anionic ligands facilitate electrochemical oxidation of the metal by stabilizing the copper(III) oxidation state: Bossu, F. P.; Chellappa, K. L.; Margerum, D. W. J. Am. Chem. Soc. 1977, 99, 2195-2203.
  • 40
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    • A copper(III) intermediate has been implicated in the decomposition of hypochlorite and hypobromite salts by anionic hydroxycuprate(II) catalysts
    • A copper(III) intermediate has been implicated in the decomposition of hypochlorite and hypobromite salts by anionic hydroxycuprate(II) catalysts: Gray, E. T. Jr.; Taylor, R. W.; Margerum, D. W. Inorg. Chem. 1977, 16, 3047-3055.
    • (1977) Inorg. Chem , vol.16 , pp. 3047-3055
    • Gray Jr., E.T.1    Taylor, R.W.2    Margerum, D.W.3
  • 41
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    • We have also ruled out a mechanism involving initial homolytic ring opening of the oxaziridine. One-electron reduction of the oxaziridine would be expected to produce a copper alkoxide and a nitrogen-centered radical, in analogy to Aubé's studies with copper(I),18 which would give rise to the opposite regiochemical outcome. Moreover, as shown in eq 5, copper(I) complexes reduce the oxaziridine but fail to produce any aminohydroxylation products, which suggests that reductive cleavage of the N-O bond is not the initial step of the mechanism
    • 18 which would give rise to the opposite regiochemical outcome. Moreover, as shown in eq 5, copper(I) complexes reduce the oxaziridine but fail to produce any aminohydroxylation products, which suggests that reductive cleavage of the N-O bond is not the initial step of the mechanism.
  • 43
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    • For reviews, see: (a) Richey, H. G. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; John Wiley: New York, 1972; III, pp 1201-1294.
    • For reviews, see: (a) Richey, H. G. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; John Wiley: New York, 1972; Vol. III, pp 1201-1294.
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    • Wiberg, K. B.; Hess, B. A., Jr.; Ashe, A. J. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; John Wiley: New York, 1972; III, pp 1295-1346.
    • (b) Wiberg, K. B.; Hess, B. A., Jr.; Ashe, A. J. In Carbonium Ions; Olah, G. A., Schleyer, P. v. R., Eds.; John Wiley: New York, 1972; Vol. III, pp 1295-1346.
  • 49
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    • The radical mechanism may also help to explain the observed reactivity of allyl silanes. Previously, we found that allyltriisopropylsilane reacts with oxaziridine 1 in the presence of Cu(TFA)2/HMPA to afford the expected aminohydroxylation product in 66% yield. However, this reaction required extended reaction times (36 h) to proceed to completion. The ability of β-silicon groups to stabilize both cations and radicals is well-known, but the former stabilization energy has been estimated to be 29-30 kcal/mol, while the latter is closer to 3-5 kcal/mol. Thus the observation that allyl silanes react more readily than primary aliphatic olefins but still require longer reaction times than styrenes is more consistent with a radical mechanism than with our originally proposed cationic mechanism. For a recent review of α- and β-silicon effects in organic synthesis, see: Chabaud, L, James, P, Landais, Y. Eur. J. Org. Chem. 2004, 3173-3199
    • 2/HMPA to afford the expected aminohydroxylation product in 66% yield. However, this reaction required extended reaction times (36 h) to proceed to completion. The ability of β-silicon groups to stabilize both cations and radicals is well-known, but the former stabilization energy has been estimated to be 29-30 kcal/mol, while the latter is closer to 3-5 kcal/mol. Thus the observation that allyl silanes react more readily than primary aliphatic olefins but still require longer reaction times than styrenes is more consistent with a radical mechanism than with our originally proposed cationic mechanism. For a recent review of α- and β-silicon effects in organic synthesis, see: Chabaud, L.; James, P.; Landais, Y. Eur. J. Org. Chem. 2004, 3173-3199.


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