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41
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8344231604
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note
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By analogy to the coupling of 8b with 12, this result can be explained by assuming that the sterically more demanding samarium alkoxy and tert-butyl groups of the intermediate ketyl radical are in equatorial positions before addition to 7.
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42
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8344263152
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unpublished results
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There has been no general success in replacing HMPA by less toxic cosolvents. In individual examples related additives (e.g. N-methylpyrrolidinone or other phosphoramide derivatives) were efficient, but unfortunately no rule has yet been recognized describing cases in which these additives are applicable. M. Berndt, S. Groß, A. Hölemann, H.-U. Reißig, unpublished results.
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Berndt, M.1
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8344282033
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note
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1H NMR spectra.
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53
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8344289188
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note
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Two equivalents of samarium diiodide are probably necessary for efficient generation of ketyl radical anions in high concentration.
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54
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0000791236
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Owing to the interaction of the σ* orbital of the C-OMe bond with the π* orbital of the terminal double bond this moiety should be able to react with nucleophiles at the terminal carbon atom. In accordance with this electronic situation, cuprates add to C-3 of alkoxyallenes: I. Marek, A. Alexakis, P. Mangeney, J.-F. Normant, Bull. Soc. Chim. Fr. 1992, 729, 171-190.
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8344232388
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note
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1H NMR spectrum (E isomer: δ = 6.37; Z isomer: δ= 6.06).
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59
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8344282799
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18]HMPA have not been performed because of the high price of this reagent.
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note
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The relative configuration of the two diastereomers could not be directly established by NMR experiments. The assignment was only possible by further transformation of 13 h into the corresponding γ-lactones (cf. 13b). See refs. [7,14]. The slight preference of the trans isomer can be rationalized by assuming that the sterically demanding samarium alkoxy and methyl groups prefer equatorial positions in the intermediate ketyl radical before adding to 12; however, since the methyl group is only a small substituent the preference for this conformation is not very large.
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