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20
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0345990427
-
-
cis-Cyclo-octene (COE) and/or cyclo-octane (COA) as well as norbornene (NBE) and/or norbornane (NBA) resulted as hydrogenation product when COD or NBD was used
-
cis-Cyclo-octene (COE) and/or cyclo-octane (COA) as well as norbornene (NBE) and/or norbornane (NBA) resulted as hydrogenation product when COD or NBD was used.
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21
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22
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0345990428
-
-
note
-
Substrate inhibition as the cause for the observed induction period can be ruled out. The induction periods also cannot be caused by neglecting to add additional hydrogen. For a substrate/precatalyst ratio of 100, there is an error of 2% expected for the complete hydrogenation of the olefin to the saturated product distributed over the entire gas uptake curve.
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23
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(a) U. Nagel, T. Krink, Angew. Chem. 105 (1993) 1099; Angew. Chem. Int. Ed. Engl. 32 (1993) 1052.
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D.G. Blackmond, T. Rosner, T. Neugebauer, M. Reetz, Angew. Chem. 111 (1999) 2333; Angew. Chem. Int. Ed. Engl. 38 (1999) 2196. 1:1 mixtures of the diastereomeric catalysts led to unexpectedly high enantioselectivities for the hydrogenation of dimethyl itaconate. These are the results of the various induction periods for the diastereomeric COD employed catalysts, so that the end effect is that the hydrogenation at first runs via a diastereomeric catalyst.
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D.G. Blackmond, T. Rosner, T. Neugebauer, M. Reetz, Angew. Chem. 111 (1999) 2333; Angew. Chem. Int. Ed. Engl. 38 (1999) 2196. 1:1 mixtures of the diastereomeric catalysts led to unexpectedly high enantioselectivities for the hydrogenation of dimethyl itaconate. These are the results of the various induction periods for the diastereomeric COD employed catalysts, so that the end effect is that the hydrogenation at first runs via a diastereomeric catalyst.
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(b) H. Brunner, W. Pieronczyk, B. Schonhammer, K. Streng, I. Bernal, J. Korp, Chem. Ber. 114 (1981) 1137. For problems encountered with RENORHOS refer to [31b]. A hydroxy derivative of NORPHOS is described in J. Ward, A. Börner, H.B. Kagan, Tetrahedron: Asymm. 3 (1992) 849.
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39
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note
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Since the partial reaction order for hydrogen, for the asymmetric reaction as well as for the diolefin hydrogenation, is one [4c] analogous results will also be obtained with other pressures.
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42
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(c) M.J. Burk, J.E. Feaster, W.A. Nugent, R.L. Harlow, J. Am. Chem. Soc. 115 (1993) 10125.
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(g) M.J. Burk, M.F. Gross, T.G.P. Harper, C.S. Kalberg, J.R. Lee, J.P. Martinez, Pure Appl. Chem. 68 (1996) 37.
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Very recently Gridnev and Imamoto have described product complexes for similar systems. I.D. Gridnev, N. Higashi, K. Asakura, T. Imamoto, J. Am. Chem. Soc. 122 (2000) 7183.
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The results obtained in the NMR tube correspond approximately to those determined in the standard hydrogenation vessel at 15.0°C (total reaction time 45 min, 99.5% ee (5) 48% COD).
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80
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0345990424
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in press
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It must be mentioned here that the NBD complexes of ligands with cyclohexyl instead of phenyl residues (DCPB 1,4-bis(dicyclohexylphosphino)butane, DCPE 1,2 bis(dicyclohexylphosphino)ethane) are still the more reactive species but also exhibit greater distortions from the square-planar arrangement (R. Kempe, A. Spannenberg, D. Heller, Z. Kristallogr. (in press). R. Kempe, A. Spannenberg, H.-J. Drexler, D. Heller, Z. Kristallogr. (in press)). The role of the cyclohexyl ligand in such situations is still unexplored.
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Z. Kristallogr.
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in press
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It must be mentioned here that the NBD complexes of ligands with cyclohexyl instead of phenyl residues (DCPB 1,4-bis(dicyclohexylphosphino)butane, DCPE 1,2 bis(dicyclohexylphosphino)ethane) are still the more reactive species but also exhibit greater distortions from the square-planar arrangement (R. Kempe, A. Spannenberg, D. Heller, Z. Kristallogr. (in press). R. Kempe, A. Spannenberg, H.-J. Drexler, D. Heller, Z. Kristallogr. (in press)). The role of the cyclohexyl ligand in such situations is still unexplored.
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The problem of induction periods is by no means restricted to asymmetric hydrogenation, but is a general phenomenon in homogeneous catalysis whenever precatalysts are used. This has been shown for the photocatalysed [2+2+2] cycloaddition of alkynes with nitriles, for instance: B. Heller, D. Heller, G. Oehme, J. Mol. Catal. A 110 (1996) 211.
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