- Olefin hydroaryloxylation catalyzed by pincer-iridium complexes
-
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 Br?nsted 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.
- Haibach, Michael C.,Guan, Changjian,Wang, David Y.,Li, Bo,Lease, Nicholas,Steffens, Andrew M.,Krogh-Jespersen, Karsten,Goldman, Alan S.
-
-
Read Online
- General, mild, and intermolecular Ullmann-type synthesis of diaryl and alkyl aryl ethers catalyzed by diol-copper(I) complex
-
(Chemical Equation Presented) A wide range of diaryl ethers and alkyl aryl ethers are synthesized through intermolecular C(aryl)-O bond formation from the corresponding aryl iodides/aryl bromides and phenols/alcohols through Ullmann-type coupling reaction in the presence of a catalytic amount of easily available (±)-diol L3-CuI complex under very mild reaction conditions. Less reactive aryl bromides can also be used for O-arylation of phenols under the same reaction conditions without increasing the reaction temperature, catalyst loading, and time. The catalytic system not only is capable of coupling hindered substrate but also tolerates a broad range of a series of functional groups.
- Naidu, Ajay B.,Jaseer,Sekar, Govindasamy
-
supporting information; experimental part
p. 3675 - 3679
(2009/09/26)
-
- Electrochemical activation of carbon dioxide: Synthesis of organic carbonates
-
Electrochemically activated CO2 reacts, under mild conditions, with primary and secondary alcohols bearing a leaving group at the α-position affording the corresponding cyclic carbonates in high yields; unsubstituted alcohols are converted, after addition of EtI, into the corresponding unsymmetrical ethyl carbonates in moderate to good yields. Tertiary alcohols and phenols are stable to the reagent.
- Casadei, M. Antonietta,Inesi, Achille,Rossi, Leucio
-
p. 3565 - 3568
(2007/10/03)
-
- New Oxidative Aromatization of α,β-Unsaturated Cyclohexenones with Iodine-Cerium(IV) Ammonium Nitrate in Alcohol
-
The reaction of 2-cyclohexen-1-one derivatives with iodine-cerium(IV) ammonium nitrate in alcohols (methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol) under refluxing, gave the corresponding alkyl phenyl ethers in good yields.In the case of diol (ethylene glycol, 1,3-propanediol, and 1,4-butanediol), phenoxyalkanol derivatives were obtained.The present method was also applicable to oxidative rearrangement of isophorone.
- Horiuchi, C. Akira,Fukunishi, Hirotada,Kajita, Mika,Yamaguchi, Akihisa,Kiyomiya, Hiroshi,Kiji, Shinji
-
p. 1921 - 1924
(2007/10/02)
-