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β-Aryl-substituted acceptors presented problems for conjugate additions of nitrogen nucleophiles: a C. Palomo, M. Oiarbide, R. Halder, M. Kelso, E. Gomez-Bengoa, J. M. Garcia, J. Am. Chem. Soc. 2004, 126, 9188-9199;
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For the reaction using the tert-butyldimethylsilyl(TBS)-protected analogue of 6c, the reaction was very sluggish and the product was isolated as single diastereomer in only 15% yield. The result indicates that the approach of the nucleophile is hindered by the steric bulk of the substrate or the TBS group is preventing the possible coordination of copper propiolate to the γ-oxygen.
-
For the reaction using the tert-butyldimethylsilyl(TBS)-protected analogue of 6c, the reaction was very sluggish and the product was isolated as single diastereomer in only 15% yield. The result indicates that the approach of the nucleophile is hindered by the steric bulk of the substrate or the TBS group is preventing the possible coordination of copper propiolate to the γ-oxygen.
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48
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34447310250
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See the Supporting Information. CCDC 635258 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif.
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See the Supporting Information. CCDC 635258 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif.
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49
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Coordination of the copper propiolate to the γ-oxygen of the acceptor may also be possible. Although the coordinating ability of organocopper reagents is considered insignificant compared to that of organolithium or -magnesium species, there is a striking reactivity difference in this reaction when the γ-oxygen is protected as TBS ether (see Ref. [12]).
-
Coordination of the copper propiolate to the γ-oxygen of the acceptor may also be possible. Although the coordinating ability of organocopper reagents is considered insignificant compared to that of organolithium or -magnesium species, there is a striking reactivity difference in this reaction when the γ-oxygen is protected as TBS ether (see Ref. [12]).
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I-catalyzed cyclization has been reported: A. Buzas, F. Gagosz, Org. Lett. 2006, 8, 515-518.
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I-catalyzed cyclization has been reported: A. Buzas, F. Gagosz, Org. Lett. 2006, 8, 515-518.
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