We have reported that sterically unhindered pincer-ligated iridium complexes, such as precursors of the fragment (iPrPCP)Ir, catalyze the addition of phenolic O-H bonds across olefin double bonds. The catalysts show very high chemo- and regio-selectivity. Notably, the chemoselectivity is very different than that displayed by Bronsted acid catalysts or catalysts that operate via a 'hidden Bronsted acid' mechanism. The mechanism of this reaction has been studied by experimental and computational methods. Moreover, in the absence of added olefin, the reactions can be catalyzed to proceed in the reverse direction, i.e. alkyl aryl ethers can be dehydroaryloxylated, giving good yields of the corresponding aryl alcohol and ether; this represents a novel catalytic C-O cleavage reaction. The dehydroaryloxylation can be further favored thermodynamically by coupling it with transfer-hydrogenation of the alkene product using a cycloalkane hydrogen donor.

Hydroaryloxylation of olefins, and C-O bond cleavage via dehydroaryloxylation of ethers, catalyzed by pincer-ligated iridium complexes

247th National Meeting (2014)

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