skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts

Authors:
 [1];  [2];  [3];  [4];  [4];  [4];  [5];  [5];  [6];  [6];  [6];  [4];  [7]
  1. Department of Chemical Physiology, The Scripps Research Institute, 10550 North Torrey Pines Road La Jolla CA 92037 USA, Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road La Jolla CA 92037 USA
  2. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road La Jolla CA 92037 USA, College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou, Nano Science and Technology, Soochow University, Suzhou 215123 P.R. China
  3. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road La Jolla CA 92037 USA, Department of Applied Chemistry, School of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310018 P.R. China
  4. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road La Jolla CA 92037 USA
  5. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley CA 94720 USA
  6. College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou, Nano Science and Technology, Soochow University, Suzhou 215123 P.R. China
  7. Department of Chemical Physiology, The Scripps Research Institute, 10550 North Torrey Pines Road La Jolla CA 92037 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1374471
Grant/Contract Number:
AC02-05CH11231; 21336005, 21176164, 21371128; 15KJA150008
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 37; Related Information: CHORUS Timestamp: 2017-08-31 06:40:35; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Wang, Hua, Zhou, Feng, Ren, Gerui, Zheng, Qinheng, Chen, Hongli, Gao, Bing, Klivansky, Liana, Liu, Yi, Wu, Bin, Xu, Qingfeng, Lu, Jianmei, Sharpless, K. Barry, and Wu, Peng. SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts. Germany: N. p., 2017. Web. doi:10.1002/ange.201701160.
Wang, Hua, Zhou, Feng, Ren, Gerui, Zheng, Qinheng, Chen, Hongli, Gao, Bing, Klivansky, Liana, Liu, Yi, Wu, Bin, Xu, Qingfeng, Lu, Jianmei, Sharpless, K. Barry, & Wu, Peng. SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts. Germany. doi:10.1002/ange.201701160.
Wang, Hua, Zhou, Feng, Ren, Gerui, Zheng, Qinheng, Chen, Hongli, Gao, Bing, Klivansky, Liana, Liu, Yi, Wu, Bin, Xu, Qingfeng, Lu, Jianmei, Sharpless, K. Barry, and Wu, Peng. Thu . "SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts". Germany. doi:10.1002/ange.201701160.
@article{osti_1374471,
title = {SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts},
author = {Wang, Hua and Zhou, Feng and Ren, Gerui and Zheng, Qinheng and Chen, Hongli and Gao, Bing and Klivansky, Liana and Liu, Yi and Wu, Bin and Xu, Qingfeng and Lu, Jianmei and Sharpless, K. Barry and Wu, Peng},
abstractNote = {},
doi = {10.1002/ange.201701160},
journal = {Angewandte Chemie},
number = 37,
volume = 129,
place = {Germany},
year = {Thu May 18 00:00:00 EDT 2017},
month = {Thu May 18 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/ange.201701160

Save / Share:
  • Cited by 5
  • In this article, the SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph 3P=N-PPh 3] +[HF 2] - as the catalyst is described. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, a remarkable diversity of monomeric building blocks was achieved by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of sidemore » chain functionalities in >99 % conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry-based post-polymerization modification.« less
  • 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. Furthermore, 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.
  • Crotonaldehyde, a chemically reactive [alpha], [beta]-unsaturated carbonyl compound, is an important industrial chemical and a ubiquitous environmental pollutant. It has been shown to be carcinogenic and mutagenic. We have studied the reaction of crotonaldehyde with nucleosides and 5'-mononucleotides and found three different types of adducts with deoxyguanosine and 2'-deoxyguanosine 5'-monophosphate. No adducts could be isolated either with nucleosides other than deoxyguanosine or with nucleotides other than 2'-deoxyguanosine 5'-monophosphate. With crotonaldehyde, deoxyguanosine produced 1, N[sup 2] and 7, 8 adducts as well as 1, N[sup 2]/7, 8 bis-adducts. The 1, N[sup 2] adducts were mixtures of diastereomers: one pair in whichmore » the substituents in the newly formed ring were trans [adduct Ia (6S, 8S) and (6R, 8R)], about 95%, and another pair Ib in which they were cis. In the case of the 7, 8-adducts IIa, b, the ribose was cleaved and a mixture of isomers in which the substituents were cis-IIa and trans-IIb (2:1) in the newly formed tetrahydropyrrole ring was observed. A 3:2 cis-IIIa and trans-IIIb mixture of 1, N[sup 2], 7, 8 bis-adducts was found with the isomerism in the newly formed tetrahydropyrrole ring in analogy to the 7, 8 adducts IIa, b. The corresponding bis-adduct with the cis form in the newly formed tetrahydropyrimidine ring was not observed. 15 refs., 2 figs., 4 tabs.« less
  • The formation of DNA adducts from (/sup 3/H)-7-hydroxymethyl-12-methylbenz(a)anthracene (7-OHM-12-MBA) and (/sup 3/H)-7,12-dimethylbenz(a)anthracene (DMBA) in the epidermis of Sencar mice was analyzed. Comparison of Sephadex LH-20 chromatographic profiles of DNA samples isolated from mice treated with DMBA or 7-OHM-12-MBA suggested that the DMBA-treated animals contained DNA adduct(s) derived from the further metabolism of 7-OHM-12-MBA. Further analysis of DNA samples from DMBA-treated mice by high-pressure liquid chromatography demonstrated the presence of 5 DNA adducts which were chromatographically indistinguishable from the DNA adducts formed in 7-OHM-12-MBA-treated mice. Epidermal homogenates were utilized to catalyze the covalent binding of (/sup 3/H)DMBA and (/sup 3/H)-7-OHM-12-MBA tomore » calf thymus DNA in vitro. Under conditions of limiting concentrations of (/sup 3/H)DMBA, the majority of the DNA adducts formed chromatographed in regions where 7-OHM-12-MBA-DNA adducts eluted. A major DMBA-DNA adduct formed in this in vitro system eluted with the same retention time as did the major 7-OHM-12-MBA-DNA adduct formed in mouse skin in vivo. These results when coupled with the in vivo data suggest that 7-OHM-12-MBA is an intermediate for at least some of the binding of DMBA to epidermal DNA in Sencar mice.« less