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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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(j) Oxidative arylation of ketone enolate: Bhowmik, D. R.; Venkateswaran, R. V. Tetrahedron Lett. 1999, 40, 7431-7433.
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Koech, P. K, Krische, M. J. J. Am. Chem. Soc. 2004, 126, 5350-5351. For a comprehensive listing of methods for α-arylation of ketones, see ref 13d
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(m) Koech, P. K.; Krische, M. J. J. Am. Chem. Soc. 2004, 126, 5350-5351. For a comprehensive listing of methods for α-arylation of ketones, see ref 13d.
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(b) Kozmin, S. A.; Iwama, T.; Huang, Y.; Rawal, V. H. J. Am. Chem. Soc. 2002, 124, 4628-4641.
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33846277017
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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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19
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24644484333
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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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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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For application to complex molecule synthesis see: d
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For application to complex molecule synthesis see: (d) MacKay, J. A.; Bishop, R. L.; Rawal, V. H. Org. Lett. 2005, 7, 3421-3424.
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33846284638
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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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25
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33748520269
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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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27
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33846300782
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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.
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Antimony enolate: (e) Kang, S. K.; Ryu, H. C.; Hong, Y. T. J. Chem. Soc., Perkin Trans. 1 2000, 3350-3351.
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Pd-catalyzed arylations of silyl ketene acetals: (a) Carfagna, C.; Musco, A.; Sallese, G.; Santi, R.; Fiorani, T. J. Org. Chem. 1991, 56, 261-263.
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33646138279
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For recent developments on Pd-catalyzed arylation of silyl enol ethers or related species, see: a, and references cited therein
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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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33846317904
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Early examples of Ni-catalyzed α-arylation of enolates: (a) Reference 2a.
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Early examples of Ni-catalyzed α-arylation of enolates: (a) Reference 2a.
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43
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0030664209
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For the Pd-catalyzed intermolecular arylation of carbonyl compounds, see: a
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and references cited therein
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Intramolecular α-arylation of enolates: (a) Muratake, H.; Natsume, M.; Nakai, H. Tetrahedron 2004, 60, 11783-11803 and references cited therein.
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Intramolecular α-arylation of enolates: (a) Muratake, H.; Natsume, M.; Nakai, H. Tetrahedron 2004, 60, 11783-11803 and references cited therein.
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54
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33846294515
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Reference 5d
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(e) Reference 5d.
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55
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0001703098
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For early reports on Pd-catalyzed alkenylation of enolates, see: a
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For early reports on Pd-catalyzed alkenylation of enolates, see: (a) Piers, E.; Marais, P. C. J. Org. Chem. 1990, 55, 3454-3455.
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See also: c, and references cited therein
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See also: (c) Yu, J. M.; Wang, T.; Liu, X. X.; Deschamps, J.; Flippen-Anderson, J.; Liao, X. B.; Cook, J. M. J. Org. Chem. 2003, 68, 7565-7581 and references cited therein.
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Bellus, D, et al, Eds, Georg Thieme: Stuttgart, Germany
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Kobayashi, S.1
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(a) Nishiyama, M.; Yamamoto, T.; Koie, Y. Tetrahedron Lett. 1998, 39, 617-620.
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Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 2123-2132. See also ref 13g.
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(d) Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 2123-2132. See also ref 13g.
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66
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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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67
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33846294880
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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.
-
-
-
-
68
-
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33846307530
-
-
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.
-
-
-
-
69
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33846289701
-
-
3P.
-
3P.
-
-
-
-
72
-
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33846289344
-
-
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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