Nucleophilic Aromatic Substitution Reactions for the Synthesis of Ferrocenyl Aryl Ethers

Marcus Korb, Pieter J. Swarts, Dominique Miesel, Alexander Hildebrandt, Jannie C. Swarts, Heinrich Lang

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

A range of ferrocenyl aryl ethers of type Fc-O-Ar (Fc = Fe(eta(5)-C6H5)(eta(5)-C6H(n)X(4-n)); n = 2-4; X = H, P(O)(OEt)(2) SO2CF3; Ar = 2,4-(NO2)(2)-C6H3, 4-NO2-C6H4) have been successfully prepared by using the nucleophilic aromatic substitution reaction (SNAr) of Fc-OLi (1a-Li) and electron-deficient aryl fluorides, enabling a new pathway to this rarely described family of organometallic compounds. Initial studies of 1a-Li and o-phosphonato-substituted hydroxyferrocenes (1b-Li) have also been performed, indicating a low nudeophilicity of the oxygen atom. The SNAr reaction protocol tolerates ortho substituents, e.g. phosphonato and sulfonyl groups, resulting in 1,2-X,O (X = S, P) ferrocenyl ethers that can be obtained in a one pot synthesis procedure including 1,3-O -> C anionic phospho- and thia-Fries rearrangements. Within these studies, the first 1,3-diortho-functionalized ferrocenyl aryl ether could be synthesized. An electrochemical study of the redox potentials of the obtained compounds allows conclusions on the reactivity of the varying electronic properties and the electrophilicity of different aryl fluorides and the nucleophilicity of the functionalized hydroxyl ferrocenes, which is directly reflected by the potential of the first ferrocene related redox processes. Chiral-pool-based phosphonates rearrange to the aryl ethers with diastereomeric excesses of 74 and 81% after the anionic Fries rearrangement. The usage of aryl 1,2-/1,3-difluorides resulted in the synthesis of the first examples of bis(FcO)-substituted benzenes. Their electrochemical investigations reveal a splitting of the two redox processes of the ferrocenyls that decreases from 155 mV (1,2-substitution) to 130 mV (1,3-substitution) on the basis of electrostatic interactions.

Original languageEnglish
Pages (from-to)1287-1300
Number of pages14
JournalOrganometallics
Volume35
Issue number9
DOIs
Publication statusPublished - 9 May 2016
Externally publishedYes

Cite this

Korb, Marcus ; Swarts, Pieter J. ; Miesel, Dominique ; Hildebrandt, Alexander ; Swarts, Jannie C. ; Lang, Heinrich. / Nucleophilic Aromatic Substitution Reactions for the Synthesis of Ferrocenyl Aryl Ethers. In: Organometallics. 2016 ; Vol. 35, No. 9. pp. 1287-1300.
@article{07f3eaf4f8064c22a216111f1db2f698,
title = "Nucleophilic Aromatic Substitution Reactions for the Synthesis of Ferrocenyl Aryl Ethers",
abstract = "A range of ferrocenyl aryl ethers of type Fc-O-Ar (Fc = Fe(eta(5)-C6H5)(eta(5)-C6H(n)X(4-n)); n = 2-4; X = H, P(O)(OEt)(2) SO2CF3; Ar = 2,4-(NO2)(2)-C6H3, 4-NO2-C6H4) have been successfully prepared by using the nucleophilic aromatic substitution reaction (SNAr) of Fc-OLi (1a-Li) and electron-deficient aryl fluorides, enabling a new pathway to this rarely described family of organometallic compounds. Initial studies of 1a-Li and o-phosphonato-substituted hydroxyferrocenes (1b-Li) have also been performed, indicating a low nudeophilicity of the oxygen atom. The SNAr reaction protocol tolerates ortho substituents, e.g. phosphonato and sulfonyl groups, resulting in 1,2-X,O (X = S, P) ferrocenyl ethers that can be obtained in a one pot synthesis procedure including 1,3-O -> C anionic phospho- and thia-Fries rearrangements. Within these studies, the first 1,3-diortho-functionalized ferrocenyl aryl ether could be synthesized. An electrochemical study of the redox potentials of the obtained compounds allows conclusions on the reactivity of the varying electronic properties and the electrophilicity of different aryl fluorides and the nucleophilicity of the functionalized hydroxyl ferrocenes, which is directly reflected by the potential of the first ferrocene related redox processes. Chiral-pool-based phosphonates rearrange to the aryl ethers with diastereomeric excesses of 74 and 81{\%} after the anionic Fries rearrangement. The usage of aryl 1,2-/1,3-difluorides resulted in the synthesis of the first examples of bis(FcO)-substituted benzenes. Their electrochemical investigations reveal a splitting of the two redox processes of the ferrocenyls that decreases from 155 mV (1,2-substitution) to 130 mV (1,3-substitution) on the basis of electrostatic interactions.",
keywords = "PHASE PARALLEL SYNTHESIS, COUPLING REACTIONS, FRIES REARRANGEMENTS, ADDITION-REACTIONS, ALKYL ETHERS, IN-SITU, C-O, COMPLEXES, REACTIVITY, DERIVATIVES",
author = "Marcus Korb and Swarts, {Pieter J.} and Dominique Miesel and Alexander Hildebrandt and Swarts, {Jannie C.} and Heinrich Lang",
year = "2016",
month = "5",
day = "9",
doi = "10.1021/acs.organomet.6b00157",
language = "English",
volume = "35",
pages = "1287--1300",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "9",

}

Korb, M, Swarts, PJ, Miesel, D, Hildebrandt, A, Swarts, JC & Lang, H 2016, 'Nucleophilic Aromatic Substitution Reactions for the Synthesis of Ferrocenyl Aryl Ethers' Organometallics, vol. 35, no. 9, pp. 1287-1300. https://doi.org/10.1021/acs.organomet.6b00157

Nucleophilic Aromatic Substitution Reactions for the Synthesis of Ferrocenyl Aryl Ethers. / Korb, Marcus; Swarts, Pieter J.; Miesel, Dominique; Hildebrandt, Alexander; Swarts, Jannie C.; Lang, Heinrich.

In: Organometallics, Vol. 35, No. 9, 09.05.2016, p. 1287-1300.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Nucleophilic Aromatic Substitution Reactions for the Synthesis of Ferrocenyl Aryl Ethers

AU - Korb, Marcus

AU - Swarts, Pieter J.

AU - Miesel, Dominique

AU - Hildebrandt, Alexander

AU - Swarts, Jannie C.

AU - Lang, Heinrich

PY - 2016/5/9

Y1 - 2016/5/9

N2 - A range of ferrocenyl aryl ethers of type Fc-O-Ar (Fc = Fe(eta(5)-C6H5)(eta(5)-C6H(n)X(4-n)); n = 2-4; X = H, P(O)(OEt)(2) SO2CF3; Ar = 2,4-(NO2)(2)-C6H3, 4-NO2-C6H4) have been successfully prepared by using the nucleophilic aromatic substitution reaction (SNAr) of Fc-OLi (1a-Li) and electron-deficient aryl fluorides, enabling a new pathway to this rarely described family of organometallic compounds. Initial studies of 1a-Li and o-phosphonato-substituted hydroxyferrocenes (1b-Li) have also been performed, indicating a low nudeophilicity of the oxygen atom. The SNAr reaction protocol tolerates ortho substituents, e.g. phosphonato and sulfonyl groups, resulting in 1,2-X,O (X = S, P) ferrocenyl ethers that can be obtained in a one pot synthesis procedure including 1,3-O -> C anionic phospho- and thia-Fries rearrangements. Within these studies, the first 1,3-diortho-functionalized ferrocenyl aryl ether could be synthesized. An electrochemical study of the redox potentials of the obtained compounds allows conclusions on the reactivity of the varying electronic properties and the electrophilicity of different aryl fluorides and the nucleophilicity of the functionalized hydroxyl ferrocenes, which is directly reflected by the potential of the first ferrocene related redox processes. Chiral-pool-based phosphonates rearrange to the aryl ethers with diastereomeric excesses of 74 and 81% after the anionic Fries rearrangement. The usage of aryl 1,2-/1,3-difluorides resulted in the synthesis of the first examples of bis(FcO)-substituted benzenes. Their electrochemical investigations reveal a splitting of the two redox processes of the ferrocenyls that decreases from 155 mV (1,2-substitution) to 130 mV (1,3-substitution) on the basis of electrostatic interactions.

AB - A range of ferrocenyl aryl ethers of type Fc-O-Ar (Fc = Fe(eta(5)-C6H5)(eta(5)-C6H(n)X(4-n)); n = 2-4; X = H, P(O)(OEt)(2) SO2CF3; Ar = 2,4-(NO2)(2)-C6H3, 4-NO2-C6H4) have been successfully prepared by using the nucleophilic aromatic substitution reaction (SNAr) of Fc-OLi (1a-Li) and electron-deficient aryl fluorides, enabling a new pathway to this rarely described family of organometallic compounds. Initial studies of 1a-Li and o-phosphonato-substituted hydroxyferrocenes (1b-Li) have also been performed, indicating a low nudeophilicity of the oxygen atom. The SNAr reaction protocol tolerates ortho substituents, e.g. phosphonato and sulfonyl groups, resulting in 1,2-X,O (X = S, P) ferrocenyl ethers that can be obtained in a one pot synthesis procedure including 1,3-O -> C anionic phospho- and thia-Fries rearrangements. Within these studies, the first 1,3-diortho-functionalized ferrocenyl aryl ether could be synthesized. An electrochemical study of the redox potentials of the obtained compounds allows conclusions on the reactivity of the varying electronic properties and the electrophilicity of different aryl fluorides and the nucleophilicity of the functionalized hydroxyl ferrocenes, which is directly reflected by the potential of the first ferrocene related redox processes. Chiral-pool-based phosphonates rearrange to the aryl ethers with diastereomeric excesses of 74 and 81% after the anionic Fries rearrangement. The usage of aryl 1,2-/1,3-difluorides resulted in the synthesis of the first examples of bis(FcO)-substituted benzenes. Their electrochemical investigations reveal a splitting of the two redox processes of the ferrocenyls that decreases from 155 mV (1,2-substitution) to 130 mV (1,3-substitution) on the basis of electrostatic interactions.

KW - PHASE PARALLEL SYNTHESIS

KW - COUPLING REACTIONS

KW - FRIES REARRANGEMENTS

KW - ADDITION-REACTIONS

KW - ALKYL ETHERS

KW - IN-SITU

KW - C-O

KW - COMPLEXES

KW - REACTIVITY

KW - DERIVATIVES

U2 - 10.1021/acs.organomet.6b00157

DO - 10.1021/acs.organomet.6b00157

M3 - Article

VL - 35

SP - 1287

EP - 1300

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 9

ER -