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0346221817
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3 (20 mol %), toluene under reflux, 16 h afforded selectively 4b in 95 % yield.
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In palladium complexes with the allyl and alkenyl tethered by a chain, the planar or perpendicular arrangements might be controlled by conformational constraints. Thus, both arrangements have been found in solution and in the solid state for a cationic complex of this type: M. E. Kraft, M. Sugiura, K. A. Aboud, J. Am. Chem. Soc. 2001, 123, 9174-9175. See also: R. Ciajolo, M. A. Jama, A. Tuzi, A. Vitagliano, J. Organomet. Chem. 1985, 295, 233-238.
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In palladium complexes with the allyl and alkenyl tethered by a chain, the planar or perpendicular arrangements might be controlled by conformational constraints. Thus, both arrangements have been found in solution and in the solid state for a cationic complex of this type: M. E. Kraft, M. Sugiura, K. A. Aboud, J. Am. Chem. Soc. 2001, 123, 9174-9175. See also: R. Ciajolo, M. A. Jama, A. Tuzi, A. Vitagliano, J. Organomet. Chem. 1985, 295, 233-238.
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0001657637
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3, the π contribution has been estimated to represent 25% of the σ-donor contribution: a) Ó. González-Blanco, V. Brachandell, Organometallics 1997, 16, 5556-5562; b) D. Woska, A. Prock, W. P. Giering, Organometallics 2000, 19, 4629-4638.
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Complex Xd has been previously studied: a) K. J. Szabó, Organometallics 1996, 15, 1128-1133; b) S. Sakaki, K. Takeuchi, M. Sugimoto, Organometallics 1997, 16, 2995-3003.
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0346221814
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note
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Other usual solvents for these reactions have similar dielectric constants (toluene 2.38, and acetic acid 6.15).
-
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67
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0346852365
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note
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-1).
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69
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0347482890
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note
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[32] However, this protocol proved to be less satisfactory than the two-step procedure used in our work.
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0346852364
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note
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An intramolecular Pd-catalyzed Oppolzer reaction provided a mixture of 7a and its trans isomer 7b, thus allowing for the NMR determination of any 7b that could have been formed from 7a. Pure 7b has been obtained by an intramolecular Pd-catalyzed coupling;
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72
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