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4344614048
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Ligand 8 was still unable to accelerate the reaction catalyzed by 1b under the optimized conditions (0 % conv., 7d, THF, 60 °C, 0.5 M); compound 1b being prepared using Kündig's protocol: E. P. Kündig, F. R. Monnier. Adv. Synth. Catal. 346, 901 (2004).
-
Ligand 8 was still unable to accelerate the reaction catalyzed by 1b under the optimized conditions (0 % conv., 7d, THF, 60 °C, 0.5 M); compound 1b being prepared using Kündig's protocol: E. P. Kündig, F. R. Monnier. Adv. Synth. Catal. 346, 901 (2004).
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43
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44649162934
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The enantiopure primary amines were commercially available or readily prepared following literature precedents, R-1,2-diphenylethanamine was obtained from the racemate using a semi-preparative CSP-HPLC resolution (Chiralpak IA, For the synthesis and absolute configuration assignment, see (a) T. Asai, T. Aoyama, T. Shioiri. Synthesis 811 (1980);
-
The enantiopure primary amines were commercially available or readily prepared following literature precedents. (R)-1,2-diphenylethanamine was obtained from the racemate using a semi-preparative CSP-HPLC resolution (Chiralpak IA). For the synthesis and absolute configuration assignment, see (a) T. Asai, T. Aoyama, T. Shioiri. Synthesis 811 (1980);
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45
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(R)-2,2-dimethyl-1-phenyl-propan-1-amine: M. E. Warren, H. E. Smith. J. Am. Chem. Soc. 87, 1757 (1965);
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44649199563
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The o-MeO substituent in 9h creates an A(1,3) strain situation with the neighboring stereogenic center; the increased rigidity of 9h vs. 9g is possibly the reason for the better selectivity. With the MeO group, 9h is also a potential tridentate ligand; the ether linkage functioning possibly as an on-off-ligand allowing for the formation of a σ-allyl Ru-intermediate. We thank a referee for this latter suggestion
-
The o-MeO substituent in 9h creates an A(1,3) strain situation with the neighboring stereogenic center; the increased rigidity of 9h vs. 9g is possibly the reason for the better selectivity. With the MeO group, 9h is also a potential tridentate ligand; the ether linkage functioning possibly as an "on-off"-ligand allowing for the formation of a σ-allyl Ru-intermediate. We thank a referee for this latter suggestion.
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44649150814
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TRISPHAT-N: [bis(tetrachlorobenzenediolato)mono(5-chloropyridine-2,3- diolato) phosphate(V)] anion. This anion 11 is chiral and was used as a racemate throughout this study.
-
TRISPHAT-N: [bis(tetrachlorobenzenediolato)mono(5-chloropyridine-2,3- diolato) phosphate(V)] anion. This anion 11 is chiral and was used as a racemate throughout this study.
-
-
-
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56
-
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44649162178
-
-
6].
-
6].
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57
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-
44649166666
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-
Compound 12 has been fully characterized using classical spectroscopic and spectrometric means. See the supplementary material.
-
Compound 12 has been fully characterized using classical spectroscopic and spectrometric means. See the supplementary material.
-
-
-
-
58
-
-
44649194771
-
-
In the absence of 3b or 12, allylic ester 4a is thermally stable at 140 °C for at least 2 h with no trace of 12 or other isomers being observed: see Table 3, entry 1
-
In the absence of 3b or 12, allylic ester 4a is thermally stable at 140 °C for at least 2 h with no trace of 12 or other isomers being observed: see Table 3, entry 1.
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34250868476
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0032275476
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Bimetallic complexes can be extremely effective catalysts in a variety of processes, see: a
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44649121811
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Compound 13, its enantiomer or the racemate, have been used successfully as ligands in many metal-catalyzed processes, see: (a) T. J. Goodwin, R. S. Vagg, P. A. Williams. J. Proc R. Soc. N. S. W. 117, 1 (1984);
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Compound 13, its enantiomer or the racemate, have been used successfully as ligands in many metal-catalyzed processes, see: (a) T. J. Goodwin, R. S. Vagg, P. A. Williams. J. Proc R. Soc. N. S. W. 117, 1 (1984);
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74
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44649121195
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-
This result reflects the intrinsic instability of ligand 13 and its complexes 14. For this reason, recycling of complexes 15 or reactions under microwave irradiation was not attempted
-
This result reflects the intrinsic instability of ligand 13 and its complexes 14. For this reason, recycling of complexes 15 or reactions under microwave irradiation was not attempted.
-
-
-
|