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. 2015 Dec 1;54(49):14866-70.
doi: 10.1002/anie.201506581. Epub 2015 Oct 22.

Branch-Selective Alkene Hydroarylation by Cooperative Destabilization: Iridium-Catalyzed ortho-Alkylation of Acetanilides

Giacomo E M Crisenza  1 , Olga O Sokolova  1 , John F Bower  2
Affiliations

Branch-Selective Alkene Hydroarylation by Cooperative Destabilization: Iridium-Catalyzed ortho-Alkylation of Acetanilides

Giacomo E M Crisenza et al. Angew Chem Int Ed Engl. .

Abstract

An iridium(I) catalyst system, modified with the wide-bite-angle and electron-deficient bisphosphine d(F) ppb (1,4-bis(di(pentafluorophenyl)phosphino)butane) promotes highly branch-selective hydroarylation reactions between diverse acetanilides and aryl- or alkyl-substituted alkenes. This provides direct and ortho-selective access to synthetically challenging anilines, and addresses long-standing issues associated with related Friedel-Crafts alkylations.

Keywords: acetanilides; branch selectivity; hydroarylation; iridium; phosphine ligands.

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Figures

Scheme 1
Scheme 1
Branch-selective hydroarylation by “cooperative destabilization” and outline of this work. BARF=tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, cod=1,5-cyclooctadiene, dFppb=1,4-bis(di(pentafluorophenyl)phosphino)butane.
Scheme 2
Scheme 2
Deuterium labeling and exchange experiments.
Scheme 3
Scheme 3
Ligand effects for the hydroarylation of styrene with 5 a.
Scheme 4
Scheme 4
Product derivatizations. dba=dibenzylideneacetone, CAN=cerium ammonium nitrate, NBS=N-bromosuccinimide, p-TSA=para-toluenesulfonic acid.
See this image and copyright information in PMC

References

    1. Rappoport Z, editor. The Chemistry of Anilines, Parts 1 and 2. New York: Wiley; 2007.
    1. Wei Z, Faul CFJ. Macromol. Rapid Commun. 2008;29:280.
    1. Lundgren RJ, Stradiotto M. Aldrichimica Acta. 2012;45:59. For a recent review on the Buchwald–Hartwig amination, see.
    1. Rao KS, Wu T-S. Tetrahedron. 2012;68:7735. For a review on the Chan–Lam coupling, see.
    1. Evano G, Blanchard N, Toumi M. Chem. Rev. 2008;108:3054. For a review that encompasses the Ullmann coupling, see. - PubMed

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