J Am Chem Soc. 2014 Sep 24;136(38):13098-101. doi: 10.1021/ja505579f. Epub 2014 Sep 15.

Linear-selective hydroarylation of unactivated terminal and internal olefins with trifluoromethyl-substituted arenes.

Journal of the American Chemical Society

Joseph S Bair, York Schramm, Alexey G Sergeev, Eric Clot, Odile Eisenstein, John F Hartwig

PMID: 25171744 DOI: 10.1021/ja505579f

Abstract

We report a series of hydroarylations of unactivated olefins with trifluoromethyl-substituted arenes that occur with high selectivity for the linear product without directing groups on the arene. We also show that hydroarylations occur with internal, acyclic olefins to yield linear alkylarene products. Experimental mechanistic data provide evidence for reversible formation of an alkylnickel-aryl intermediate and rate-determining reductive elimination to form the carbon-carbon bond. Labeling studies show that formation of terminal alkylarenes from internal alkenes occurs by initial establishment of an equilibrating mixture of alkene isomers, followed by addition of the arene to the terminal alkene. Computational (DFT) studies imply that the aryl C-H bond transfers to a coordinated alkene without oxidative addition and support the conclusion from experiment that reductive elimination is rate-determining and forms the anti-Markovnikov product. The reactions are inverse order in α-olefin; thus the catalytic reaction occurs, in part, because isomerization creates a low concentration of the reactant α-olefin.

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• Journal Article