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33745412649
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The configuration on the phosphorus center of a PdI2 complex is described by e.g. (S,SMp)-12-Pd, the configuration on the phosphorus center of the ligand displaced from this complex is described by (S,RP)-12. The change of the Cahn, Ingold Prelog descriptor (SMP → RP) on going from the PdI2 complex to the ligand (same configuration on the phosphorus center) is due to this nomenclature.
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The configuration on the phosphorus center of a PdI2 complex is described by e.g. (S,SMp)-12-Pd, the configuration on the phosphorus center of the ligand displaced from this complex is described by (S,RP)-12. The change of the Cahn, Ingold Prelog descriptor (SMP → RP) on going from the PdI2 complex to the ligand (same configuration on the phosphorus center) is due to this nomenclature.
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chapter 9 and ref. [6].
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and literature cited. VPC values, found for couplings to C-4 and C-2 carbon atoms in diastereomeric (S,Rp)-13, (S,Sp)-l3 ligands can be used for confomational studies'7". A large Jpc constant suggests a small dihedral angle between the lone electron pair and the carbon atom. From this rule combined with a study of molecular models we could unambiguously derive the correct configuration at the phosphorus center.
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J. H. Nelson, Coord. Client. Rev. 1995,139, 245-280 and literature cited. VPC values, found for couplings to C-4 and C-2 carbon atoms in diastereomeric (S,Rp)-13, (S,Sp)-l3 ligands can be used for confomational studies'7". A large Jpc constant suggests a small dihedral angle between the lone electron pair and the carbon atom. From this rule combined with a study of molecular models we could unambiguously derive the correct configuration at the phosphorus center.
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36
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0008451370
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and réf.'61 . With our PdI2 complexes an optimum optical yield of 10% ee is reached.
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T. Hayashi, M. Konishi, M. Fukushima, K. Kanehira, T. Hioki, M. Kumada, J. Org. Client. 1983, 48, 2195-2202 and réf.'61 . With our PdI2 complexes an optimum optical yield of 10% ee is reached.
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J. Org. Client.
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Hayashi, T.1
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52
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33745333941
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J Different chemical shifts and JPC values, assigned to each carbon atom are due to restricted rotation about the N-acyl bond (cf. réf." ). All I3C{'H}-NMR spectra were measured at 298 K.
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J Different chemical shifts and JPC values, assigned to each carbon atom are due to restricted rotation about the N-acyl bond (cf. réf." ). All I3C{'H}-NMR spectra were measured at 298 K.
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33745395174
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Different chemical shifts and JPC values, assigned to each carbon atom are due to the diastereomeric mixture. They can be classed with each of the two diastereomers in those cases, when separation is feasible (tertiary phosphanes).
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Different chemical shifts and JPC values, assigned to each carbon atom are due to the diastereomeric mixture. They can be classed with each of the two diastereomers in those cases, when separation is feasible (tertiary phosphanes).
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1H}NMR (10Q.62 MHz, 298 K): 4 d for (C-2)-(C-4) [2 diastereomers, each with 2 rotamers (slow interconversion of rotamers on the NMR time scale)]. 13C{'H}NMR (62.9 MHz, 298 K): coalescence spectrum with broad resonances for (C-2)-(C-4). 13C{1H}NMR (20.15 MHz, 298 K): 2 d for (C-2)-(C-4) [2 diastereomers (fast interconversion of rotamers on the NMR time scale)].
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1H}NMR (10Q.62 MHz, 298 K): 4 d for (C-2)-(C-4) [2 diastereomers, each with 2 rotamers (slow interconversion of rotamers on the NMR time scale)]. 13C{'H}NMR (62.9 MHz, 298 K): coalescence spectrum with broad resonances for (C-2)-(C-4). 13C{1H}NMR (20.15 MHz, 298 K): 2 d for (C-2)-(C-4) [2 diastereomers (fast interconversion of rotamers on the NMR time scale)].
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0000671139
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|