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.
| Original language | English |
|---|---|
| Pages (from-to) | 15062-15070 |
| Number of pages | 9 |
| Journal | Journal of the American Chemical Society |
| Volume | 135 |
| Issue number | 40 |
| DOIs | |
| Publication status | Published - 2013 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Olefin hydroaryloxylation catalyzed by pincer-iridium complexes. / Haibach, Michael C.; Guan, Changjian; Wang, David Y.; Li, Bo; Lease, Nicholas; Steffens, Andrew M.; Krogh-Jespersen, Karsten; Goldman, Alan S.
In: Journal of the American Chemical Society, Vol. 135, No. 40, 2013, p. 15062-15070.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Olefin hydroaryloxylation catalyzed by pincer-iridium complexes
AU - Haibach, Michael C.
AU - Guan, Changjian
AU - Wang, David Y.
AU - Li, Bo
AU - Lease, Nicholas
AU - Steffens, Andrew M.
AU - Krogh-Jespersen, Karsten
AU - Goldman, Alan S
PY - 2013
Y1 - 2013
N2 - 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.
AB - 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.
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U2 - 10.1021/ja404566v
DO - 10.1021/ja404566v
M3 - Article
VL - 135
SP - 15062
EP - 15070
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 40
ER -