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Volumn 50, Issue 13, 2011, Pages 2990-2994

Stereospecific copper-catalyzed C-H allylation of electron-deficient arenes with allyl phosphates

Author keywords

Allylation; C H functionalization; Copper; Fluoroarenes; Stereospecificity

Indexed keywords

ACETYLACETONATES; AROMATIC CORES; C-H FUNCTIONALIZATION; CHEMICAL EQUATIONS; COPPER COMPLEXES; ELECTRON-DEFICIENT; FLUOROARENES; PHENANTHROLINES; STEREOSPECIFIC; STEREOSPECIFIC MANNER; STEREOSPECIFICITY;

EID: 79952655564     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201007733     Document Type: Article
Times cited : (136)

References (112)
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    • Hoarau and co-workers reported a palladium-catalyzed direct coupling of oxazole-4-carboxylate with allyl chlorides. However, the corresponding alkenylated products were isolated as a result of the concomitant olefin isomerization
    • Hoarau and co-workers reported a palladium-catalyzed direct coupling of oxazole-4-carboxylate with allyl chlorides. However, the corresponding alkenylated products were isolated as a result of the concomitant olefin isomerization: C. Verrier, C. Hoarau, F. Marsais, Org. Biomol. Chem. 2009, 7, 647.
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    • For selected works on the copper-mediated direct C-H functionalization, see: a) Z. Li, C.-J. Li, J. Am. Chem. Soc. 2006, 128, 56;
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    • note
    • Without copper catalysts, the product was detected in less than 2%yield (determined by gas chromatography analysis). See the Supporting Information for the detailed optimization studies.
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    • N2′ selectivity whilst the diaryl cuprate resulted in a mixture of regioisomers
    • N2′ selectivity whilst the diaryl cuprate resulted in a mixture of regioisomers: a) J.-E. Bäckvall, M. Sellén, B. Grant, J. Am. Chem. Soc. 1990, 112, 6615;
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    • note
    • For base-assisted direct cupration, see Ref. [6h,j,k], [8], and [9c,j,l,m].
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    • note
    • 2]/phen had little influence on the regio- and stereochemical outcomes and they possessed lower catalytic activity.
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    • N2′ product 3ai′ with high E selectivity was observed (see the following equation). For an addition/elimination pathway in the metal-catalyzed allylic substitution, see: Ref. [1e,h,j]. (Chemical Equation Presented)
    • N2′ product 3ai′ with high E selectivity was observed (see the following equation). For an addition/elimination pathway in the metal-catalyzed allylic substitution, see: H. Ohmiya, U. Yokoi, Y. Makida, M. Sawamura, J. Am. Chem. Soc. 2010, 132, 2895; Ref. [1e,h,j]. (Chemical Equation Presented)
    • (2010) J. Am. Chem. Soc. , vol.132 , pp. 2895
    • Ohmiya, H.1    Yokoi, U.2    Makida, Y.3    Sawamura, M.4
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    • note
    • An initial study into the application to 1,3,4-oxadiazole was successful (see the following equation). Attempts to apply the present copper catalytic systems to other acidic azoles such as benzoxazole, benzothiazole, and benzimidazole were unsuccessful (<2% yield by gas chromatography analysis. Further optimization and details will be reported in due course. (Chemical Equation Presented)


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