An Efficient Organocatalyzed Interconversion of Silyl Ethers to Tosylates Using DBU and <i>p</i>-Toluenesulfonyl Fluoride

Gembus, Vincent; Marsais, Francis; Levacher, Vincent

doi:10.1055/s-2008-1078407

Cited by 105 publications

(116 citation statements)

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“…1), producing aryl sulfonates. [10] We in turn found that fluorosulfates react with aryl silyl ethers under similar conditions, forming diorganosulfates (eq. 2).…”

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confidence: 99%

SuFEx‐Based Synthesis of Polysulfates

et al. 2014

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A handful of high fidelity reactions are at the core of industrial processes producing polymers in multimillion-ton quantities. Most commodity polymers are synthesized from olefins by forming carbon-carbon backbones, whereas engineering polymers are commonly prepared via condensation reactions of monomers often containing an activated carbonyl group or its equivalent and a suitable nucleophile, thus forming carbon-heteroatom linkages. Polyesters, polyamides, polyurethanes, and polyimides are produced in this manner. Despite the variety of backbone structures, polymers containing sulfur(VI) "-SO 2 -" connectors are virtually absent from the literature and are barely used in industrial applications (with the exception of polysulfones, in which the sulfone group is already present in the monomers [1] ).Unsurprisingly, most reported attempts to synthesize sulfur(VI)-containing polymers relied on reactions mimicking carbonyl group-based condensations, i.e. reactions of sulfonyl chlorides with nucleophiles [2] and, to a much lesser extent, Friedel-Crafts sulfonylations. [3] While polymers obtained by those methods can have attractive properties, such as good thermal and hydrolytic stability and mechanical resilience, [2c-e] the unselective reactivity of sulfur(VI) chlorides, which are susceptible to hydrolysis and participate in redox transformations and radical chlorinations, significantly limit the utility of these methods and materials.Sulfur(VI) fluorides, in particular sulfuryl fluoride (SO 2 F 2 ) and its monofluorinated derivatives, sulfonyl (RSO 2 -F) fluorides, sulfamoyl (R 2 NSO 2 -F) fluorides, and fluorosulfates (ROSO 2 -F) stand in stark contrast to other sulfur(VI) halides. These sulfur oxofluorides are much more hydrolytically stable, redox silent, and do not act as halogenating agents. Nevertheless, their selective reactivity can be revealed when an * fokin@scripps.edu Homepage: http://www.scripps.edu/fokin; sharples@scripps.edu Homepage: http://www.scripps.edu/sharpless. Supporting information for this article is available on the WWW under http://www.angewandte.org or from the authors. The formation of sulfonyl-heteroatom bonds is described in detail in an accompanying article in this issue. [5] In the early 1970s, Firth pioneered the synthesis of poly(arylsulfate) polymers from fluorosulfates of Bisphenol A (BPA), which he obtained from SO 2 F 2 , and disodium salts of the bisphenol. [6] Preparation of these monomers required prolonged heating, and pure high polymer was obtained only after repeated precipitation. Here, we report a simple and straightforward SuFEx-based method for the synthesis of high molecular weight polysulfate polymers from aryl fluorosulfates and aryl silyl ethers under simple and mild reaction conditions. HHS Public AccessReactions of silylated and fluorinated compounds are, of course, well known in organic synthesis [7] and in polymer chemistry. [8] For example, in 1983, Kricheldorf introduced the "silyl method" for the synthesis of polyaryl ethers taking advantage of the str...

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“…1), producing aryl sulfonates. [10] We in turn found that fluorosulfates react with aryl silyl ethers under similar conditions, forming diorganosulfates (eq. 2).…”

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confidence: 99%

SuFEx‐Based Synthesis of Polysulfates

et al. 2014

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“…In this work, we exploited the exquisite reactivity of the sulfur(VI) fluoride moiety toward aryl silyl ethers, a facet of sulfur fluoride exchange (SuFEx) chemistry that was first reported by Gembus 19 and further developed by Sharpless and our laboratories eq 1 and 2. 20,21 SuFEx was also recently exploited for the postmodification of polymer brushes on surfaces, 22 work highly related and complementary to our own herein.…”

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confidence: 99%

Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions

2016

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Functional polystyrenes and polyacrylamides, containing combinations of fluorosulfate, aromatic silyl ether, and azide side chains, were used as scaffolds to demonstrate the postpolymerization modification capabilities of sulfur(VI) fluoride exchange (SuFEx) and CuAAC chemistries. Fluorescent dyes bearing appropriate functional groups were sequentially attached to the backbone of the copolymers, quantitatively and selectively addressing their reactive partners. This combined SuFEx and CuAAC approach proved to be robust and versatile, allowing for a rare accomplishment: triple orthogonal functionalization of a copolymer under essentially ambient conditions without protecting groups.

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“…Moreover, the S VI eF group can be specifically reacted with certain functional groups (e.g. silane, secondary amine) to eliminate the fluorine while forming a stable sulfuryl linkage (eSO 2 e) between the two components [36,38,39], which demonstrates the potential of using these reactions in linking chemistry. These SuFEx reactions have been demonstrated to be orthogonal, metal-catalyst-free, efficient (i.e.…”

Section: Introductionmentioning

confidence: 99%

Combination of AGET ATRP and SuFEx for post-polymerization chain-end modifications

Beringer

Chen

et al. 2015

Polymer

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a b s t r a c tPost-polymerization modification of polymer chain-ends is a powerful tool for the preparation of functional materials. "Click" type reactions represent the most prevalent post-polymerization strategies. We applied the recently described sulfur(VI) fluoride exchange reaction to functionalize the chain-ends of four polymers prepared using activators generated by electron transfer atom transfer radical polymerization. Aryl-TBDMS terminated polymers were reacted with aryl sulfurofluoridate compounds with a near quantitative conversion. This research represents the application of a new click type reaction to prepare functional polymers.

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An Efficient Organocatalyzed Interconversion of Silyl Ethers to Tosylates Using DBU and p-Toluenesulfonyl Fluoride

Cited by 105 publications

References 1 publication

SuFEx‐Based Synthesis of Polysulfates

SuFEx‐Based Synthesis of Polysulfates

Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions

Combination of AGET ATRP and SuFEx for post-polymerization chain-end modifications

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