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Hydrogen‐Borrowing and Interrupted‐Hydrogen‐Borrowing Reactions of Ketones and Methanol Catalyzed by Iridium
Author(s) -
Shen Di,
Poole Darren L.,
Shotton Camilla C.,
Kornahrens Anne F.,
Healy Mark P.,
Donohoe Timothy J.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201410391
Subject(s) - nucleophile , chemistry , catalysis , ketone , methanol , phosphine , iridium , hydrogen , denticity , ligand (biochemistry) , enone , organic chemistry , photochemistry , medicinal chemistry , combinatorial chemistry , biochemistry , receptor , crystal structure
Reported herein is the use of catalytic [{Ir(cod)Cl} 2 ] to facilitate hydrogen‐borrowing reactions of ketone enolates with methanol at 65 °C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. Subsequent addition of pro‐nucleophiles to the reaction mixture allowed a one‐pot methylenation/conjugate addition protocol to be developed, which greatly expands the range of products that can be made by this methodology.