Olefin hydroaryloxylation catalyzed by pincer-iridium complexes

Michael C. Haibach, Changjian Guan, David Y. Wang, Bo Li, Nicholas Lease, Andrew M. Steffens, Karsten Krogh-Jespersen, Alan S Goldman

Research output: Contribution to journalArticle

33 Citations (Scopus)

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 languageEnglish
Pages (from-to)15062-15070
Number of pages9
JournalJournal of the American Chemical Society
Volume135
Issue number40
DOIs
Publication statusPublished - 2013

Fingerprint

Iridium
Alkenes
Olefins
Ethers
Ether
Catalysts
Chemical Industry
Atoms
Catalyst selectivity
Organometallics
Chemical industry
Transition metals
Metals
Acids

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Haibach, M. C., Guan, C., Wang, D. Y., Li, B., Lease, N., Steffens, A. M., ... Goldman, A. S. (2013). Olefin hydroaryloxylation catalyzed by pincer-iridium complexes. Journal of the American Chemical Society, 135(40), 15062-15070. https://doi.org/10.1021/ja404566v

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 journalArticle

Haibach, MC, Guan, C, Wang, DY, Li, B, Lease, N, Steffens, AM, Krogh-Jespersen, K & Goldman, AS 2013, 'Olefin hydroaryloxylation catalyzed by pincer-iridium complexes', Journal of the American Chemical Society, vol. 135, no. 40, pp. 15062-15070. https://doi.org/10.1021/ja404566v
Haibach MC, Guan C, Wang DY, Li B, Lease N, Steffens AM et al. Olefin hydroaryloxylation catalyzed by pincer-iridium complexes. Journal of the American Chemical Society. 2013;135(40):15062-15070. https://doi.org/10.1021/ja404566v
Haibach, Michael C. ; Guan, Changjian ; Wang, David Y. ; Li, Bo ; Lease, Nicholas ; Steffens, Andrew M. ; Krogh-Jespersen, Karsten ; Goldman, Alan S. / Olefin hydroaryloxylation catalyzed by pincer-iridium complexes. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 40. pp. 15062-15070.
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