Structural and synthetic insights into sodium‐mediated‐ferration of fluoroarenes

Maddock, Lewis C. H. and Kennedy, Alan R. and Hevia, Eva (2021) Structural and synthetic insights into sodium‐mediated‐ferration of fluoroarenes. Helvetica Chimica Acta, 104 (12). e2100206. ISSN 0018-019X (https://doi.org/10.1002/hlca.202100206)

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Abstract

Exploiting chemical cooperation between Na and Fe(II) within the bimetallic base [dioxane ⋅ NaFe(HMDS) 3] (I), (dioxane=1,4-dioxane, HMDS=N(SiMe 3) 2) the selective ferration of fluorobenzene, 1-fluoronaphthalene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1-bromo-3,5-difluorobenzene, 3-fluoroanisole and 3,5-difluoroanisole has been realized, affording sodium ferrates [dioxane ⋅ Na(HMDS)(2-F-C 6H 4)Fe(HMDS)] ∞ (1), [dioxane ⋅ Na(HMDS)(2-F-C 10H 6)Fe(HMDS)] ∞ (2), [dioxane ⋅ {Na(HMDS)(2,5-F 2-C 6H 3)Fe(HMDS)} 2] ∞ (3), [dioxane ⋅ {Na(HMDS)(2,3,6-F 3-C 6H 2)Fe(HMDS)} 2] ∞ (4), [(dioxane) 1.5 ⋅ Na(HMDS)(2,4,6-F 3-C 6H 2)Fe(HMDS)] 2 (5), [(dioxane) 1.5 ⋅ {Na(HMDS)(4-Br-2,6-F 2-C 6H 2)Fe(HMDS) 2] (6), [{(dioxane) 2 ⋅ Na 2Fe(HMDS) 2(2-methoxy-6-F-C 6H 3)} +{Fe(HMDS) 3} −] ∞ (7) and [dioxane ⋅ {Na(HMDS)(4-methoxy-2,6-F 2-C 6H 2)Fe(HMDS)} 2] ∞ (8), respectively. Reactions take place under mild reaction conditions, with excellent control of the selectivity and no competing C−F bond activation is observed. Showcasing complex polymeric arrangements in some cases, the structures of compounds 1–8 have been determined by X-ray crystallographic studies. In all cases, the Fe(II) centers occupy the position in the relevant fluoroarene that was previously filled by a proton, confirming that these metallations are actually ferration processes whereas the Na atoms prefer to form Na⋅⋅⋅F dative interactions. Compounds 1–8 are thermally stable and do not undergo benzyne formation (through NaF elimination) and their formation contrasts with the inertness of Fe(HMDS) 2 which fails to act as a base to metallate fluoroarenes.

ORCID iDs

Maddock, Lewis C. H., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015 and Hevia, Eva;
  • Item type:Article
    ID code:78659
    Dates:
    Date
    Event
    1 December 2021
    Published
    29 October 2021
    Published Online
    25 October 2021
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:23 Nov 2021 09:54
    Last modified:11 Nov 2024 13:17
    URI:https://strathprints.strath.ac.uk/id/eprint/78659
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