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J Am Chem Soc. 2013 Jan 16;135(2):751-62. doi: 10.1021/ja309176h. Epub 2013 Jan 8.

Nickel-catalyzed reductive conjugate addition to enones via allylnickel intermediates.

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  • 1Department of Chemistry, University of Rochester, Rochester, New York 14627-0216, USA.


An alternative method to copper-catalyzed conjugate addition followed by enolate silylation for the synthesis of β-disubstituted silyl enol ether products (R(1)(R(2))HCCH═C(OSiR(4)(3))R(3)) is presented. This method uses haloarenes instead of nucleophilic aryl reagents. Nickel ligated to either neocuproine or bipyridine couples an α,β-unsaturated ketone or aldehyde (R(2)HC═CHC(O)R(3)) with an organic halide (R(1)-X) in the presence of a trialkylchlorosilane reagent (Cl-SiR(4)(3)). Reactions are assembled on the benchtop and tolerate a variety of functional groups (aldehyde, ketone, nitrile, sulfone, pentafluorosulfur, and N-aryltrifluoroacetamide), electron-rich iodoarenes, and electron-poor haloarenes. Mechanistic studies have confirmed the first example of a catalytic reductive conjugate addition of organic halides that proceeds via an allylnickel intermediate. Selectivity is attributed to (1) rapid, selective reaction of LNi(0) with chlorotriethylsilane and enone in the presence of other organic electrophiles, and (2) minimization of enone dimerization by ligand steric effects.

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