Volume 18, Issue 8 p. 2423-2429
Full Paper

Fe-Catalyzed Multicomponent Reactions: The Regioselective Alkoxy Allylation of Activated Olefins and its Application in Sequential Fe Catalysis

Dipl.-Chem. Dipl.-Ing. André P. Dieskau

Dipl.-Chem. Dipl.-Ing. André P. Dieskau

Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany), Fax: (+49) 711-685 64285

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Dipl.-Chem. Michael S. Holzwarth

Dipl.-Chem. Michael S. Holzwarth

Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany), Fax: (+49) 711-685 64285

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Prof. Dr. Bernd Plietker

Corresponding Author

Prof. Dr. Bernd Plietker

Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany), Fax: (+49) 711-685 64285

Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany), Fax: (+49) 711-685 64285Search for more papers by this author
First published: 16 January 2012
Citations: 45

Graphical Abstract

Iron adds it: Allylic carbonates react with various activated olefins in an Fe-catalyzed decarboxylative alkoxy allylation to afford densely substituted products in good yields and with high regioselectivities under mild conditions (see scheme). The robustness of the catalytic system is demonstrated by the first Fe-catalyzed alkoxy allylation allylic sulfenylation and three-component coupling sequence.

Abstract

We present herein a versatile and broadly applicable Fe-catalyzed regioselective alkoxy allylation of activated double bonds. Substituted allylic carbonates are converted into the corresponding σ-enyl Fe complexes by reaction with Bu4N[Fe(CO)3(NO)] (TBAFe) at 30 °C. The liberated alkoxide adds to an activated double bond with the generation of a C-nucleophile, which is trapped by the σ-enyl Fe complex in a regioselective manner. Alternatively, the alkoxide acts as a base in deprotonating an external pronucleophile, which undergoes Michael addition. The method is characterized by a broad functional group tolerance, mild reaction conditions, low catalyst loadings, and high regioselectivities in favor of the ipso-substitution product.