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DOI: 10.1055/s-2008-1042696
Nickel-Catalyzed Regioselective Olefin-Directed Cross-Coupling Reaction
Contributor(s):Mark Lautens, Valentina AureggiColorado State University, Fort Collins, USA
Alkene-Directed Regioselective Nickel-Catalyzed Cross-Coupling of Cyclic Anhydrides with Diorganozinc Reagents
Angew. Chem. Int. Ed. 2007, 46: 9301-9304
Publication History
Publication Date:
21 February 2008 (online)
Key words
nickel - diorganozinc reagents - cross-coupling
Significance
The development of an efficient catalytic regioselective alkylation of cyclic anhydrides through olefin-directed nickel insertion and subsequent cross-coupling is reported. The corresponding alkylated products are obtained in good yields and regioselectivities.
Review
For previous work using styrenic additives, see: J. B. Johnson, E. A. Bercot, J. M. Rowley, G. W. Coates, T. Rovis J. Am. Chem. Soc. 2007, 129, 2718.
Comment
The authors demonstrate the ability of olefins, terminal or internal, to direct the cross-coupling of cyclic anhydrides with diorganozinc nucleophiles. The alkylation of bicyclic succinic anhydrides which contain both a terminal and an internal olefin occurs with high regioselectivity at the side of the terminal olefin. The substrate needs cis conformation between the olefin and the anhydride moiety. In the absence of terminal alkenes, internal olefins are also efficient directing groups to provide the desired products in good yields and high regioselectivities. This transformation is also selective in the presence of two terminal olefins differentiated by a methylene spacer in which the most proximal olefin directs the alkylation.