title: Olefin hydroaryloxylation catalyzed by pincer-iridium complexes.
abstract: Aryl alkyl ethers, which are widely used throughout the chemical industry, are typically produced via the Williamson ether synthesis. Olefin hydroaryloxylation potentially offers a much more atom-economical alternative. Known acidic catalysts for hydroaryloxylation, however, afford very poor selectivity. We report the organometallic-catalyzed intermolecular hydroaryloxylation of unactivated olefins by iridium "pincer" complexes. These catalysts do not operate via the hidden Brønsted acid pathway common to previously developed transition-metal-based catalysts. The reaction is proposed to proceed via olefin insertion into an iridium-alkoxide bond, followed by rate-determining C-H reductive elimination to yield the ether product. The reaction is highly chemo- and regioselective and offers a new approach to the atom-economical synthesis of industrially important ethers and, potentially, a wide range of other oxygenates.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors.forename: Michael C
authors.initials: MC
authors.lastname: Haibach
authors.forename: Changjian
authors.initials: C
authors.lastname: Guan
authors.forename: David Y
authors.initials: DY
authors.lastname: Wang
authors.forename: Bo
authors.initials: B
authors.lastname: Li
authors.forename: Nicholas
authors.initials: N
authors.lastname: Lease
authors.forename: Andrew M
authors.initials: AM
authors.lastname: Steffens
authors.forename: Karsten
authors.initials: K
authors.lastname: Krogh-Jespersen
authors.forename: Alan S
authors.initials: AS
authors.lastname: Goldman