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Volumn 8, Issue 25, 2006, Pages 5725-5728

Palladium-catalyzed regiocontrolled α-arylation of trimethylsilyl enol ethers with aryl halides

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE; BROMIDE; CHLORIDE; HALOGEN; IODIDE; ORGANOTIN COMPOUND; PALLADIUM; TOLUENE; TRIBUTYLTIN; TRIMETHYLSILYL DERIVATIVE;

EID: 33846214325     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol062093g     Document Type: Article
Times cited : (53)

References (73)
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    • Selected examples of α-arylation of ketones that do not involve Pd catalysis: (a) Semmelhack, M. F.; Chong, B. P.; Stauffer, R. D.; Rogerson, T. D.; Chong, A.; Jones, L. D. J. Am. Chem. Soc. 1975, 97, 2507-2516.
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    • The direct o-nitroarylation of enolates with aryliodonium salts has also been reported: Rawal, V. H.; Takenaka, N.; Iwama, T. Abstracts of Papers; 222nd National Meeting of the American Chemical Society, Chicago, IL, August 26-30, 2001; American Chemical Society: Washington, DC, 2001; ORGN-007 (for a detailed abstract, see Chem. Abstr. AN 2001:640370).
    • (b) The direct o-nitroarylation of enolates with aryliodonium salts has also been reported: Rawal, V. H.; Takenaka, N.; Iwama, T. Abstracts of Papers; 222nd National Meeting of the American Chemical Society, Chicago, IL, August 26-30, 2001; American Chemical Society: Washington, DC, 2001; ORGN-007 (for a detailed abstract, see Chem. Abstr. AN 2001:640370).
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    • For a full discussion of this work, see: Takenaka, N. Ph.D. Dissertation, University of Chicago, Chicago, IL, 2002. For a related report, see: (c) Aggarwal, V. K.; Olofsson, B. Angew. Chem., Int. Ed. 2005, 44, 5516-5519.
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    • The contents of this paper were presented at the 222nd National Meeting of the American Chemical Society: Rawal, V. H.; Iwama, T. Abstracts of Papers; 222nd National Meeting of the American Chemical Society, Chicago, IL, August 26-30, 2001; American Chemical Society: Washington, DC, ORGN-606 (for a detailed abstract, see Chem. Abstr. AN 2001:640969). This work was also presented at the 33rd Great Lakes/Central Regional Meeting of the American Chemical Society, Grand Rapids, MI, June 11-13, 2001.
    • The contents of this paper were presented at the 222nd National Meeting of the American Chemical Society: Rawal, V. H.; Iwama, T. Abstracts of Papers; 222nd National Meeting of the American Chemical Society, Chicago, IL, August 26-30, 2001; American Chemical Society: Washington, DC, ORGN-606 (for a detailed abstract, see Chem. Abstr. AN 2001:640969). This work was also presented at the 33rd Great Lakes/Central Regional Meeting of the American Chemical Society, Grand Rapids, MI, June 11-13, 2001.
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    • A recent publication by Verkade, Hartwig, and co-workers, describing the use of similar conditions, that appeared on the web prompts us to present fully our previously reported work (ref 6) in this area. See: Su, W.; Raders, S.; Verkade, J. G.; Liao, X.; Hartwig, J. F. Angew. Chem., Int. Ed. 2006, 45, 5852-5855.
    • A recent publication by Verkade, Hartwig, and co-workers, describing the use of similar conditions, that appeared on the web prompts us to present fully our previously reported work (ref 6) in this area. See: Su, W.; Raders, S.; Verkade, J. G.; Liao, X.; Hartwig, J. F. Angew. Chem., Int. Ed. 2006, 45, 5852-5855.
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    • Other early examples of Pd-catalyzed α-arylation that go through stannyl enolates: (a) Kosugi, M.; Sizuki, M.; Hagiwara, I.; Goto, K.; Saitho, K.; Migita, T. Chem. Lett. 1982, 939-940.
    • Other early examples of Pd-catalyzed α-arylation that go through stannyl enolates: (a) Kosugi, M.; Sizuki, M.; Hagiwara, I.; Goto, K.; Saitho, K.; Migita, T. Chem. Lett. 1982, 939-940.
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    • For recent developments on Pd-catalyzed arylation of silyl enol ethers or related species, see: (a) Hama, T.; Culkin, D. A.; Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 4976-4985, and references cited therein.
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    • Early examples of Ni-catalyzed α-arylation of enolates: (a) Reference 2a.
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    • This combination was selected as it was expected to be a challenging arylation, since not only is the phenylation cyclohexanone reported to be low yielding ref 8, but the oxidative addition to the electron-rich p-iodoanisole was expected to be slow
    • This combination was selected as it was expected to be a challenging arylation, since not only is the phenylation cyclohexanone reported to be low yielding (ref 8), but the oxidative addition to the electron-rich p-iodoanisole was expected to be slow.
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    • An extensive screening of reaction conditions was carried out. Pd sources examined: PdCl2(Ph3P)2, PdCl 2(o-Tol3P)2, PdCl2, Pd 2(dba)3, Pd(OAc)2, or PtCl2(PhCN) 2. Phosphine ligands: BINAP. Tol-BINAP, t- Bu3P, t-BuCH2)3P, 2-(di-tert-butylphosphino) biphenyl, cHex3P, Ph3P, o-Tol) 3As, Ph3As, and (i-PrO)3P. Fluoride sources: Bu3SnF, LiF, NaF, CsF, CuF2, ZnF2, ZrF4, KF, ZnCl2, SnCl4, or Me4NF. Solvents: benzene, toluene, DMF, or THF. Additives: LiCl, NaOAc and t-BuOK
    • 4NF. Solvents: benzene, toluene, DMF, or THF. Additives: LiCl, NaOAc and t-BuOK.
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    • 4), and concentrated. The residue was purified by flash column chromatography on silica gel.
    • 4), and concentrated. The residue was purified by flash column chromatography on silica gel.
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    • 3P.
    • 3P.
  • 72
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    • 1H NMR of the crude reaction mixture. Product 5 was assigned the trans stereochemistry based on the coupling constant of the 2,3-vicinal protons (J = 11.5 Hz).
    • 1H NMR of the crude reaction mixture. Product 5 was assigned the trans stereochemistry based on the coupling constant of the 2,3-vicinal protons (J = 11.5 Hz).


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