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

Abstract

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 side 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.

Authors:
 [1];  [2];  [3];  [4];  [4];  [4];  [5];  [5];  [6];  [6];  [6];  [4];  [7]
  1. The Scripps Research Inst., La Jolla, CA (United States). Dept. of Chemical Physiology and Dept. of Chemistry
  2. The Scripps Research Inst., La Jolla, CA (United States). Dept. of Chemistry; Soochow Univ., Suzhou (China). College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou, Nano Science and Technology
  3. The Scripps Research Inst., La Jolla, CA (United States). Dept. of Chemistry; Zhejiang Univ., Hangzhou (China). Dept. of Applied Chemistry and School of Food Science and Biotechnology
  4. The Scripps Research Inst., La Jolla, CA (United States). Dept. of Chemistry
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry
  6. Soochow Univ., Suzhou (China). College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou, Nano Science and Technology
  7. The Scripps Research Inst., La Jolla, CA (United States). Dept. of Chemical Physiology
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); National Institutes of Health (NIH); National Natural Science Foundation of China (NNSF); National Basic Research Program of China
OSTI Identifier:
1425415
Alternate Identifier(s):
OSTI ID: 1374472
Grant/Contract Number:  
AC02-05CH11231; CHE 1610987; R01GM113046; 21336005; 21176164; 21371128; 15KJA150008
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 37; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; bifluoride salt; click chemistry; ethenesulfonyl fluoride; polysulfonate formation; SuFEx reaction

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. United States: N. p., 2017. Web. doi:10.1002/anie.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. United States. doi:10.1002/anie.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". United States. doi:10.1002/anie.201701160. https://www.osti.gov/servlets/purl/1425415.
@article{osti_1425415,
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 = {In this article, the SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph3P=N-PPh3]+[HF2]- 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 side 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.},
doi = {10.1002/anie.201701160},
journal = {Angewandte Chemie (International Edition)},
number = 37,
volume = 56,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

Click Chemistry: Diverse Chemical Function from a Few Good Reactions
journal, June 2001


A Stepwise Huisgen Cycloaddition Process: Copper(I)-Catalyzed Regioselective �Ligation� of Azides and Terminal Alkynes
journal, July 2002


Peptidotriazoles on Solid Phase� [1,2,3]-Triazoles by Regiospecific Copper(I)-Catalyzed 1,3-Dipolar Cycloadditions of Terminal Alkynes to Azides
journal, May 2002

  • Torn�e, Christian W.; Christensen, Caspar; Meldal, Morten
  • The Journal of Organic Chemistry, Vol. 67, Issue 9, p. 3057-3064
  • DOI: 10.1021/jo011148j

A Stepwise Huisgen Cycloaddition Process: Copper(I)-Catalyzed Regioselective �Ligation� of Azides and Terminal Alkynes
journal, July 2002