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For some reviews on the copper-catalysed carbon-heteroatom bond formation, see: a
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For some reviews on the copper-catalysed carbon-heteroatom bond formation, see: a) S. V. Ley, A. W. Thomas, Angew. Chem. 2003, 115, 5558-5607;
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a) K. R. Bley, R. D. Clark, A. Jahangir, (F. Hoffmann-La Roche AG, CH) WO 2005/005394 A2, 2005
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c) G. Liu, J. R. Huth, E. T. Olejniczak, R. Mendoza, P. DeVries, S. Leitza, E. B. Reilly, G. F. Okasinski, S. W. Fesik, T. W. Von Geldern, J. Med. Chem. 2001, 44, 1202-1210;
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DeVries, P.5
Leitza, S.6
Reilly, E.B.7
Okasinski, G.F.8
Fesik, S.W.9
Von Geldern, T.W.10
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d) G. Liu, J. T. Link, Z. Pei, E. B. Reilly, S. Leitza, B. Nguyen, K. C. Marsh, G. F. Okasinski, T. W. von Geldern, M. Ormes, K. Fowler, M. Gallatin, J. Med. Chem. 2000, 43, 4025-4040;
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Liu, G.1
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Pei, Z.3
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Okasinski, G.F.8
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Pinchart, A.1
Dallaire, C.2
Gingras, M.3
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For some copper-catalysed S-arylation examples, see: a
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For some copper-catalysed S-arylation examples, see: a) C. Palomo, M. Oiarbide, R. López, E. Gómez-Bengoa, Tetrahedron Lett. 2000, 41, 1283-1286;
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Palomo, C.1
Oiarbide, M.2
López, R.3
Gómez-Bengoa, E.4
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0037043523
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palladium has also been reported to effect such transformation, see
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b) C. G. Bates, R. K. Gujadhur, D. Venkataraman, Org. Lett. 2002, 4, 2803-2806; palladium has also been reported to effect such transformation, see:
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Org. Lett
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Bates, C.G.1
Gujadhur, R.K.2
Venkataraman, D.3
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13
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3342908633
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M. Murata, S. L. Buchwald, Tetrahedron 2004, 60, 7397-7403; a few examples of nickel-catalysed S-arylation of thiols have also been described:
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d) M. Murata, S. L. Buchwald, Tetrahedron 2004, 60, 7397-7403; a few examples of nickel-catalysed S-arylation of thiols have also been described:
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14
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0000073247
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e) V. Percec, J. Y. Bae, D. H. Hill, J. Org. Chem. 1995, 60, 6895-6903.
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Percec, V.1
Bae, J.Y.2
Hill, D.H.3
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15
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20544435104
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For some recent reviews on the utility of on-water chemistry in organic synthesis, see: a
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For some recent reviews on the utility of "on-water" chemistry in organic synthesis, see: a) S. Narayan, J. Muldoon, M. G. Finn, V. V. Fokin, H. C. Kolb, K. B. Sharpless, Angew. Chem. 2005, 117, 3339-3343;
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Narayan, S.1
Muldoon, J.2
Finn, M.G.3
Fokin, V.V.4
Kolb, H.C.5
Sharpless, K.B.6
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20344388819
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Angew. Chem. Int. Ed. 2005, 44, 3275-3279;
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Chem. Int. Ed
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b) C.-J. Li, Chem. Rev. 2005, 105, 3095-3165;
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Li, C.-J.1
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M. Carril, R. SanMartin, I. Tellitu, E. Domínguez, Org. Lett. 2006, 8, 1467-1470.
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Carril, M.1
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Domínguez, E.4
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20
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34250859918
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For the appropriate use of terms such as in/on water and in the presence of water, see: Y. Hayashi, Angew. Chem. 2006, 118, 8281-8282;
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For the appropriate use of terms such as "in/on water" and "in the presence of water", see: Y. Hayashi, Angew. Chem. 2006, 118, 8281-8282;
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21
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33845788846
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Angew. Chem. Int. Ed. 2006, 45, 8103-8104.
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Chem. Int. Ed
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Angew1
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34250823338
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This observation is in contrast with the results obtained in our previously reported protocol for the synthesis of benzo[b]furans. In that case, the basicity of the diamine was more relevant and TMEDA provided better yields for the target compounds than rani-1,2-diaminecyclohexane. See ref, 5
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This observation is in contrast with the results obtained in our previously reported protocol for the synthesis of benzo[b]furans. In that case, the basicity of the diamine was more relevant and TMEDA provided better yields for the target compounds than (rani-1,2-diaminecyclohexane. See ref. [5].
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34250902248
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It is assumed that the oxidation state for in situ generated copper complexes in this type of reactions is +1 and +3. see ref, 1b, Nevertheless, it is also known that copper(I) could dissociate to copper(0) and (II, However, no evidence of copper(0) precipitation has been observed while performing the target reaction
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It is assumed that the oxidation state for in situ generated copper complexes in this type of reactions is +1 and +3. see ref. [1b]. Nevertheless, it is also known that copper(I) could dissociate to copper(0) and (II). However, no evidence of copper(0) precipitation has been observed while performing the target reaction.
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-1. Lower yields were observed when using other dilution values.
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-1. Lower yields were observed when using other dilution values.
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34250894228
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To understand better the process it should be borne in mind that the species that dissolve in the aqueous phase are probably not the starting materials as such, but ionic species derived from them. For instance, in the case of the thiol, the soluble specie would be the corresponding thiolate. For the aryl halide. however, it is plausible that the water-soluble copper catalyst may also be soluble in the organic phase so that the oxidative addition step of the aryl halide may take place in the organic layer. Thus, if so, the species prone to dissolve in the water phase would be a copper complex holding the corresponding aryl fragment, but not directly the aryl halide. However, there are no experimental evidences to support these hypotheses
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To understand better the process it should be borne in mind that the species that dissolve in the aqueous phase are probably not the starting materials as such, but ionic species derived from them. For instance, in the case of the thiol, the soluble specie would be the corresponding thiolate. For the aryl halide. however, it is plausible that the water-soluble copper catalyst may also be soluble in the organic phase so that the oxidative addition step of the aryl halide may take place in the organic layer. Thus, if so, the species prone to dissolve in the water phase would be a copper complex holding the corresponding aryl fragment, but not directly the aryl halide. However, there are no experimental evidences to support these hypotheses.
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34250806391
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S. L. Buchwald, A. Klapars, F. Y. Kwong, E. Streiter, J. Zanon (Massachusetts Institute of Technology, US). WO 2004/013094 A2, 2004
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S. L. Buchwald, A. Klapars, F. Y. Kwong, E. Streiter, J. Zanon (Massachusetts Institute of Technology, US). WO 2004/013094 A2, 2004
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Although inconclusive, the initial results obtained from atomic absorption analysis show that up to a 3% of the initial amount of copper is lost from the aqueous solution during the first run and subsequent extraction. Therefore it is assumable that further runs and extractions will have similar or even worse effects for the survival of the initial copper catalyst
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Although inconclusive, the initial results obtained from atomic absorption analysis show that up to a 3% of the initial amount of copper is lost from the aqueous solution during the first run and subsequent extraction. Therefore it is assumable that further runs and extractions will have similar or even worse effects for the survival of the initial copper catalyst.
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and references therein
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P. Barbaro, Chem. Eur. J. 2006, 12, 5666-5675. and references therein.
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