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For example trigonal copper(I) olefin complexes such as those described in this paper might serve as steric models of the palladium(0) intermediates following the transition state of asymmetric allylic alkylation. See: a) S. Ramdeehul, P. Dierkes, R. Aquado, P. C. Kamer, P. W. N. M. van Leeuwen, J. A. Osborn, Angew. Chem. 1998, 110, 3302; Angew. Chem. Int. Ed. 1998, 37, 3118; b) E. Peña-Cabrera, P.-O. Norrby, M. Sjögren, A. Vitagliano, V. De Felice, J. Oslob, S. Ishii, D. O'Neill, B. Åkermark, P. Elquist, J. Am. Chem. Soc. 1996, 118, 4299.
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5544240942
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note
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The diamine 1 was always used in almost enantiomerically pure form. It was prepared and resolved by us and both (S,S)-1 and (R,R)-1 enantiomers were available. Most experiments were performed using (S,S)-1 but in some cases the R, R enantiomer was used. To avoid confusion in presenting the results, throughout this paper we consistently refer to the use of (S,S)-1.
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27
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5544228515
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Although allowed by symmetry, the alternate possibility, S, S, S, S, is too unlikely on steric grounds to be considered as the configuration of a major species.
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5544221493
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note
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2+ ion were present.
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36
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5544228509
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note
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Confusion should be avoided by keeping in mind that according to the re-si nomenclature convention, a formal inversion takes place in going from propene to any higher α-olefin. That is, the same enantioface that is named re in the propene molecule, is named si in the case of higher olefins and vice-versa.
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5544258607
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2, respectively, while in the platinum complex the corresponding distance is 4.2 Å.
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41
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5544326718
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note
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A further decrease in stability of the asymmetric R, S, S, S configuration is observed in the case of allylic alcohols and ethers (see Table 1) and can also be rationalized. Since in this arrangement the copper ion is hindered on one side of the coordination plane, the interactions with the counterion or solvent on the "open" side should be stronger, thus leaving less room for the intramolecular interaction with the alcoholic oxygen and reducing the overall relative stability compared with the symmetric configuration R, S, S, R.
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42
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5544244952
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note
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Hydrogen bonding between the OH group and the counterion (possibly occurring in close-tight ion pairs) is not relevant for the chiral recognition of the R enantiomer, since substitution of a methoxy group for the oxydryl in the 3-methoxy-1-butene complex 10 did not affect the selectivity.
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43
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5544303986
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Guerra, G.1
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