Synlett 2020; 31(10): 945-952
DOI: 10.1055/s-0039-1691745
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© Georg Thieme Verlag Stuttgart · New York

Synthesis of Aromatic and Aliphatic Di-, Tri-, and Tetrasulfonic Acids

Jens Christoffers
a   Institut für Chemie, Carl von Ossietzky Universität Oldenburg, 26111 Oldenburg, Germany   Email: jens.christoffers@uol.de
,
Mathias S. Wickleder
b   Department für Chemie, Universität zu Köln, 50939 Köln, Germany   Email: mathias.wickleder@uni-koeln.de
› Author Affiliations
Financial support from the Deutsche Forschungsgemeinschaft (Grant No. CH157/17 and WI1842/11) is gratefully acknowledged.
Further Information

Publication History

Received: 15 January 2020

Accepted after revision: 13 February 2020

Publication Date:
17 March 2020 (online)


Abstract

Oligosulfonic acids are promising linker compounds for coordination polymers and metal-organic frameworks, however, compared to their carboxylic acid congeners, often not readily accessible by established synthetic routes. This Account highlights the synthesis of recently developed aromatic and aliphatic di-, tri- and tetrasulfonic acids. While multiple electrophilic sulfonations of aromatic substrates are rather limited, the nucleophilic aromatic substitution including an intramolecular variant, the Newman–Kwart rearrangement, allows the flexible introduction of up to four sulfur-containing moieties at an aromatic ring. Sulfonic acids are then accessed by oxidation of thiols, thioethers, or thioesters either directly with hydrogen peroxide or in two steps with chlorine (generated in situ from N-chlorosuccinimide/hydrochloric acid) to furnish sulfochlorides which are subsequently hydrolyzed. In the aliphatic series, secondary alcohols as starting materials are converted into thioethers, thioesters, or thiocarbonates by nucleophilic substitutions, which are also subsequently oxidized to furnish sulfonic acids.

1 Introduction

2 Electrophilic Aromatic Substitution

3 Nucleophilic Aromatic Substitution

3.1 Intermolecular SNAr

3.2 Intermolecular with Subsequent Oxidation

3.3 Intramolecular with Subsequent Oxidation

4 Nucleophilic Aliphatic Substitution with Subsequent Oxidation

5 Oxidation

5.1 Oxidation of Thiocarbonates

5.2 Oxidation of Thioethers

5.3 Oxidation of Thioesters

6 Thermolysis of Neopentylsulfonates

7 Functionalization via Diazonium Ions

8 Conclusion