Abstract
Despite broad interest in metal carbene complexes, there remain few examples of catalytic transformations of ethers that proceed via alkoxycarbene intermediates generated by α,α-dehydrogenation. We demonstrate that both neutral and cationic alkoxycarbene derivatives are accessible via ether dehydrogenation at a PNP(iPr)4 pincer-supported iridium complex (PNP(iPr)4 = 2,6-bis((diisopropylphosphino)methyl)pyridine). Both cationic and neutral alkoxycarbene complexes undergo group transfer imination with azides, with the cationic derivative serving as a more efficient catalyst for cyclopentyl ether imination. Mechanistic studies support an iridium(I)dinitrogen complex as the resting state in the dark and a role for light-promoted N2 dissociation. Isoamyl nitrite and phenyl ethyl ketene are also found to engage with the cationic alkoxycarbene complex in formal alkoxide and O atom transfer reactions, respectively. In the former case an isolable dialkoxyalkyliridium complex is obtained, representing only the second example of a structurally characterized dialkoxyalkyl complex of a transition metal.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
