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Iterative arylation of itaconimides with diazonium salts through electrophilic Palladium catalysis : divergent β-H-elimination pathways in repetitive Matsuda-Heck reactions
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Riemer, Nastja, Shipman, Michael, Wessig, Pablo and Schmidt, Bernd (2019) Iterative arylation of itaconimides with diazonium salts through electrophilic Palladium catalysis : divergent β-H-elimination pathways in repetitive Matsuda-Heck reactions. The Journal of Organic Chemistry, 84 (9). pp. 5732-5746. doi:10.1021/acs.joc.9b00627 ISSN 0022-3263.
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WRAP-iterative-arylation-itaconimides-diazonium-salts-through-electrophilic-Palladium-catalysis-Shipman-2019.pdf - Accepted Version - Requires a PDF viewer. Download (727Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/acs.joc.9b00627
Abstract
N-Arylitaconimides, accessible from maleic anhydride, anilines and paraformaldehyde, react with arene diazonium salts in a Pd-catalyzed Matsuda-Heck arylation to the pharmacologically relevant E-configured 3-arylmethylidene pyrrolidine-2,5-diones (also known as arylmethylidene succinimides) through an exo-selective β-H-elimination. The coupling proceeds at ambient temperature with the simple and easy-to-handle precatalyst Pd-II-acetate under ligand- and base-free conditions. Notable features are high isolated yields as well as regio- and stereoselectivities, and short reaction times. In a comparative investigation, aryl iodides, bromides and triflates were shown to be inferior coupling reagents in this reaction. The 3-arylmethylidene pyrrolidine-2,5-diones undergo a second Matsuda-Heck coupling, which proceeds via an endo-selective β-H-elimination to give diarylmethyl substituted maleimides as coupling products. These products can also be accessed in one flask by sequential addition of different arene diazonium salts to the starting itaconimide. The potential of 3-arylmethylidene succinimides as photoswitches was tested. Upon irradiation of the E-isomer at 300 nm partial isomerization to the Z-isomer (E : Z = 65 : 35 in the photostationary state) was observed. The isomerization was found to be nearly completely reversible by irradiating the mixture at 400 nm.
Item Type: | Journal Article | ||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||
Library of Congress Subject Headings (LCSH): | Palladium catalysts, Arylation | ||||||||
Journal or Publication Title: | The Journal of Organic Chemistry | ||||||||
Publisher: | American Chemical Society | ||||||||
ISSN: | 0022-3263 | ||||||||
Official Date: | 3 May 2019 | ||||||||
Dates: |
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Volume: | 84 | ||||||||
Number: | 9 | ||||||||
Page Range: | pp. 5732-5746 | ||||||||
DOI: | 10.1021/acs.joc.9b00627 | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Reuse Statement (publisher, data, author rights): | This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.9b00627 | ||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||
Date of first compliant deposit: | 18 April 2019 | ||||||||
Date of first compliant Open Access: | 16 April 2020 |
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