2014
DOI: 10.1002/ange.201403758
|View full text |Cite
|
Sign up to set email alerts
|

SuFEx‐Based Synthesis of Polysulfates

Abstract: 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 m… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1
1

Citation Types

2
48
0
3

Year Published

2014
2014
2022
2022

Publication Types

Select...
8

Relationship

4
4

Authors

Journals

citations
Cited by 105 publications
(53 citation statements)
references
References 25 publications
2
48
0
3
Order By: Relevance
“…In addition, the SuFEx process has proven itself reliable for polymer synthesis such as the preparation of robust poly(diarylsulfonate) thermoplastic materials. [7]…”
Section: Sulfonyl Fluorides Vs Other Sulfonyl Halidesmentioning
confidence: 99%
See 1 more Smart Citation
“…In addition, the SuFEx process has proven itself reliable for polymer synthesis such as the preparation of robust poly(diarylsulfonate) thermoplastic materials. [7]…”
Section: Sulfonyl Fluorides Vs Other Sulfonyl Halidesmentioning
confidence: 99%
“…A wide variety of functional groups can be tolerated (Figure 13 B), limited only by steric bulk at silicon and the presence of acidic protons that can quench the basic catalyst. The process therefore has many characteristics of a click reaction and so is suitable for the synthesis of polymeric materials, such as the sulfate analogue [7,115] of the well-known poly(bisphenol A carbonate) (Lexan, CAS# 25037-45-2) shown in Figure 13 C. Additional iterations of this new polymerization process are described in a recent report by Dong et al [7] This conversion of aromatic silyl ethers into fluorosulfates and diarylsulfates is quite different from the popular use of silyl sulfonates (usually triflates) as catalysts in processes such as acetalization, [132] aldol, and allylation reactions. [133] In these and many other cases, silicon-oxygen bonds are swapped, or SiÀC is exchanged for SiÀO.…”
Section: Synthesis and Reactivity Of Fluorosulfates (Roso 2 F): Silicmentioning
confidence: 99%
“…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. The SuFEx reactions, in combination with CuAAC eq 3, provide a robust and modular platform for selective modification of polymers and/or other materials.…”
Section: ■ Introductionmentioning
confidence: 84%
“…[7] SuFEx reliably allows the flawless substitution of S VI ÀF with aryl silyl ethers to give S VI ÀObonds,and with amines to give S VI À Nbonds.While the mechanistic details are yet to be fully elucidated, these transactions are made possible by as pecial co-action between the hydrogen-bonding environment of fluoride ion, and the kinetic and thermodynamic properties of the bonds to sulfur(VI) and silicon centers.Key to SuFEx activation is the requirement for fluoride to transit from as trong covalent bond to al eaving group-a process mediated by tertiary amine derived catalysts [8] and thought to involve the bifluoride ion and related species. [7,[9][10][11][12][13] Early in the development of SuFEx, we identified sulfuryl fluoride (SO 2 F 2 ) [7,14] as as ulfur(VI) hub for creating diaryl sulfate links between molecules.Under SuFEx conditions,the latent reactivity of the otherwise stable S VI À Fbond is roused to react with SuFExable substrates. [7,15] While SuFEx is still an emerging technology it has already found diverse applications including,f or example:t he synthesis of tosylates [9] and sulfonyl azides; [10] application in polymer chemistry [11] and post-polymerization modification; [12,13] Suzuki coupling of aryl-and heteroaryl-fluorosulfates with boronic acids.…”
mentioning
confidence: 99%
“…[7,[9][10][11][12][13] Early in the development of SuFEx, we identified sulfuryl fluoride (SO 2 F 2 ) [7,14] as as ulfur(VI) hub for creating diaryl sulfate links between molecules.Under SuFEx conditions,the latent reactivity of the otherwise stable S VI À Fbond is roused to react with SuFExable substrates. [7,15] While SuFEx is still an emerging technology it has already found diverse applications including,f or example:t he synthesis of tosylates [9] and sulfonyl azides; [10] application in polymer chemistry [11] and post-polymerization modification; [12,13] Suzuki coupling of aryl-and heteroaryl-fluorosulfates with boronic acids. [15] Of particular significance,h owever,i st he potential for SuFEx in biochemical applications: growing evidence supports the notion that proteins provide molecular and dynamic electrostatic field environments that sulfur(VI) fluoride linkages are adept at reading,and reacting to.…”
mentioning
confidence: 99%