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67049108133
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note
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Enantioselectivities of up to 94% can be achieved with in-situ-formed Rh/bppm catalysts under optimised conditions.
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18
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67049118376
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manuscript in preparation
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Details of the NMR spectroscopic assignment will be given separately, S. Lange, W. Leitner, R. Mynott and C. Wirtz, manuscript in preparation.
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Lange, S.1
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19
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37049082532
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13C-NMR spectroscopy in deuterium labelling studies, see (a) J. M. Brown, A. E. Derome, G. D. Hughes and P. K. Monaghan, Aust. J. Chem., 1992, 45, 143; (b) J. K. MacDougall, M. C. Simpson and D. J. Cole-Hamilton, J. Chem. Soc., Dalton Trans., 1994, 3061.
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67049088910
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note
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67049169520
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note
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The major exception are catalysts with chiral ligands forming five-membered chelates, as the corresponding rhodium complexes are not e3ective for the formyl C-H bond cleavage.
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26
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67049096875
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note
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An alternative explanation involving rhodacylobutane intermediates was put forward to rationalise the change of vicinal to 1,3-addition during transfer hydrogenation of 1a or 1b in aqueous media. Although we cannot rule out this possibility, it does not provide a satisfactory explanation for the decisive influence of the allylic carboxyl group and the preferred incorporation of protons at C-1.
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33
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67049173297
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note
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Acidic hydrolysis proved less suitable. Control experiments showed that no measureable H/D exchange in product 5 occurred under the basic conditions.
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