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  Dialkyl Ether Formation at High-Valent Nickel

Le Vaillant, F., Reijerse, E. J., Leutzsch, M., & Cornella, J. (2020). Dialkyl Ether Formation at High-Valent Nickel. Journal of the American Chemical Society, 142(46), 19540-19550. doi:10.1021/jacs.0c07381.

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 Creators:
Le Vaillant, Franck1, Author              
Reijerse, Edward J.2, Author
Leutzsch, Markus3, Author              
Cornella, Josep1, Author              
Affiliations:
1Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2466693              
2Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34−36, Mülheim an der Ruhr 45470, Germany, ou_persistent22              
3Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              

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 Abstract: In this article, we investigated the I2-promoted cyclic dialkyl ether formation from 6-membered oxanickelacycles originally reported by Hillhouse. A detailed mechanistic investigation based on spectroscopic and crystallographic analysis revealed that a putative reductive elimination to forge C(sp3)–OC(sp3) using I2 might not be operative. We isolated a paramagnetic bimetallic NiIII intermediate featuring a unique Ni2(OR)2 (OR = alkoxide) diamond-like core complemented by a μ-iodo bridge between the two Ni centers, which remains stable at low temperatures, thus permitting its characterization by NMR, EPR, X-ray, and HRMS. At higher temperatures (>−10 °C), such bimetallic intermediate thermally decomposes to afford large amounts of elimination products together with iodoalkanols. Observation of the latter suggests that a C(sp3)–I bond reductive elimination occurs preferentially to any other challenging C–O bond reductive elimination. Formation of cyclized THF rings is then believed to occur through cyclization of an alcohol/alkoxide to the recently forged C(sp3)–I bond. The results of this article indicate that the use of F+ oxidants permits the challenging C(sp3)–OC(sp3) bond formation at a high-valent nickel center to proceed in good yields while minimizing deleterious elimination reactions. Preliminary investigations suggest the involvement of a high-valent bimetallic NiIII intermediate which rapidly extrudes the C–O bond product at remarkably low temperatures. The new set of conditions permitted the elusive synthesis of diethyl ether through reductive elimination, a remarkable feature currently beyond the scope of Ni.

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Language(s): eng - English
 Dates: 2020-07-142020-11-042020-11-18
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.0c07381
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 142 (46) Sequence Number: - Start / End Page: 19540 - 19550 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870