Polymerizations of 2-(Trimethylsilyl)ethanesulfonyl-activated aziridines

Qu, Taoguang; Rupar, Paul A.

doi:10.1016/j.eurpolymj.2022.111135

Polymerizations of 2-(Trimethylsilyl)ethanesulfonyl-activated aziridines

Journal Article · Sat Mar 12 00:00:00 EST 2022 · European Polymer Journal

DOI:https://doi.org/10.1016/j.eurpolymj.2022.111135· OSTI ID:1977120

Qu, Taoguang ^[1]; Rupar, Paul A. ^[2]

University of Alabama, Tuscaloosa, AL (United States); OSTI
University of Alabama, Tuscaloosa, AL (United States)

A novel N-sulfonyl aziridine, N-((2-(trimethylsilyl)ethyl)sulfonyl)-2-methyl-aziridine (SES-MeAz) was synthesized, and its controlled anionic ring-opening polymerization to form poly(SES-MeAz) studied. The desulfonylation of poly(SES-MeAz)s can be achieved under mild conditions, with tetrabutylammonium fluoride (TBAF) to form polypropylene imine (PPI), although purification of the PPI was not completely successful. The block copolymer p(pTs-MeAz)-b-p(SES-MeAz), (pTs-MeAz = N-para-tosyl-2-methyl-aziridine) was prepared by a sequential polymerization. The desulfonylation of the block copolymer is the first example of the selective removal of a sulfonyl protecting group from a poly(sulfonylazirdine) block copolymer and this is the first formation of a polysufonylaziridine-block-polypropylene imine copolymer. Three-armed star-shaped poly(SES-MeAz)s were also successfully synthesized and exhibited improved solubility compared with linear poly(SES-MeAz)s.

View Accepted Manuscript (DOE)

Research Organization:: University of Alabama, Tuscaloosa, AL (United States); University of South Alabama, Mobile, AL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC); University of Alabama

Grant/Contract Number:: SC0020282

OSTI ID:: 1977120

Journal Information:: European Polymer Journal, Journal Name: European Polymer Journal Journal Issue: C Vol. 169; ISSN 0014-3057

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Controlling the Polymer Microstructure in Anionic Polymerization by Compartmentalization Rieger, Elisabeth; Blankenburg, Jan; Grune, Eduard Angewandte Chemie International Edition, Vol. 57, Issue 9 https://doi.org/10.1002/anie.201710417	journal	January 2018
Well‐Defined Poly(Ester Amide)‐Based Homo‐ and Block Copolymers by One‐Pot Organocatalytic Anionic Ring‐Opening Copolymerization of N ‐Sulfonyl Aziridines and Cyclic Anhydrides Xu, Jiaxi; Hadjichristidis, Nikos Angewandte Chemie International Edition, Vol. 60, Issue 13 https://doi.org/10.1002/anie.202015339	journal	February 2021
Direct Access to L-Azetidine-2-carboxylic Acid Bouazaoui, M'barek; Martinez, Jean; Cavelier, Florine European Journal of Organic Chemistry, Vol. 2009, Issue 17 https://doi.org/10.1002/ejoc.200900233	journal	June 2009
Recent advances in rational gene transfer vector design based on poly(ethylene imine) and its derivatives Neu, Michael; Fischer, Dagmar; Kissel, Thomas The Journal of Gene Medicine, Vol. 7, Issue 8 https://doi.org/10.1002/jgm.773	journal	January 2005
Aziridine Termination of Living Anionic Polymerization Thomi, Laura; Wurm, Frederik R. Macromolecular Rapid Communications, Vol. 35, Issue 5 https://doi.org/10.1002/marc.201300860	journal	February 2014
Sequence-Controlled Polymers via Simultaneous Living Anionic Copolymerization of Competing Monomers Rieger, Elisabeth; Alkan, Arda; Manhart, Angelika Macromolecular Rapid Communications, Vol. 37, Issue 10 https://doi.org/10.1002/marc.201600092	journal	April 2016
Influence of branching architecture on polymer properties Zhu, Xinyuan; Zhou, Yongfeng; Yan, Deyue Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 18 https://doi.org/10.1002/polb.22320	journal	July 2011
Soluble polymers in water purification Bolto, B. Progress in Polymer Science, Vol. 20, Issue 6 https://doi.org/10.1016/0079-6700(95)00010-D	journal	January 1995
Facile synthesis of sulfonyl chlorides Huang, Jianxing; Widlanski, Theodore S. Tetrahedron Letters, Vol. 33, Issue 19 https://doi.org/10.1016/S0040-4039(00)79050-2	journal	May 1992
β-Trimethylsilylethanesulfonyl chloride (SES-Cl): A new reagent for protection of amines Weinreb, Steven M.; Demko, Donald M.; Lessen, Thomas A. Tetrahedron Letters, Vol. 27, Issue 19 https://doi.org/10.1016/S0040-4039(00)84458-5	journal	January 1986
Grafting polysulfonamide from cellulose paper through organocatalytic ring-opening polymerization of N-sulfonyl aziridines Zhu, Linlin; Chen, Qinyong; Wang, Ying Carbohydrate Polymers, Vol. 261 https://doi.org/10.1016/j.carbpol.2021.117903	journal	June 2021
Expanding the scope of N-heterocyclic carbene-organocatalyzed ring-opening polymerization of N-tosyl aziridines using functional and non-activated amine initiators Bakkali-Hassani, Camille; Rieger, Elisabeth; Vignolle, Joan European Polymer Journal, Vol. 95 https://doi.org/10.1016/j.eurpolymj.2017.07.005	journal	October 2017
Copolymerization of aziridines and cyclic anhydrides by metal-free catalysis strategy Xia, Tian; Yue, Tian-Jun; Gu, Ge-Ge European Polymer Journal, Vol. 136 https://doi.org/10.1016/j.eurpolymj.2020.109900	journal	August 2020
Tetrabutylammonium fluoride initiated anionic ring-opening polymerizations of N–sulfonyl aziridines Wang, Haixin; Li, Jie; Li, Zhenjiang European Polymer Journal, Vol. 140 https://doi.org/10.1016/j.eurpolymj.2020.109999	journal	November 2020
N-heterocyclic olefins catalyzed ring-opening polymerization of N-tosyl aziridines Zhou, Li; Wang, Zhenyu; Xu, Guangqiang European Polymer Journal, Vol. 140 https://doi.org/10.1016/j.eurpolymj.2020.110046	journal	November 2020
Major degradable polycations as carriers for DNA and siRNA Islam, Mohammad Ariful; Park, Tae‐Eun; Singh, Bijay Journal of Controlled Release, Vol. 193 https://doi.org/10.1016/j.jconrel.2014.05.055	journal	November 2014
Synthesis and arylation of unprotected sulfonimidamides Funes Maldonado, Matías; Sehgelmeble, Fernando; Bjarnemark, Fanny Tetrahedron, Vol. 68, Issue 36 https://doi.org/10.1016/j.tet.2012.06.072	journal	September 2012
Organocatalytic Synthesis of Polysulfonamides with Well-Defined Linear and Brush Architectures from a Designed/Synthesized Bis( N -sulfonyl aziridine) Zhu, Linlin; Huang, Huishan; Wang, Ying Macromolecules, Vol. 54, Issue 17 https://doi.org/10.1021/acs.macromol.1c01193	journal	August 2021
Anionic Ring-Opening Polymerizations of N -Sulfonylaziridines in Ionic Liquids Giri, Chandan; Sisk, Sarah E.; Reisman, Louis Macromolecules, Vol. 55, Issue 2 https://doi.org/10.1021/acs.macromol.1c01885	journal	January 2022
Polymerizations of Nitrophenylsulfonyl-Activated Aziridines Mbarushimana, Pierre Canisius; Liang, Qiaoli; Allred, Jared M. Macromolecules, Vol. 51, Issue 3 https://doi.org/10.1021/acs.macromol.7b02125	journal	January 2018
Selective Initiation from Unprotected Aminoalcohols for the N -Heterocyclic Carbene-Organocatalyzed Ring-Opening Polymerization of 2-Methyl- N- tosyl Aziridine: Telechelic and Block Copolymer Synthesis Bakkali-Hassani, Camille; Coutouly, Clément; Gleede, Tassilo Macromolecules, Vol. 51, Issue 7 https://doi.org/10.1021/acs.macromol.7b02493	journal	March 2018
Diaziridyl Ether of Bisphenol A Kang, Seohyun; Moon, Hyun Kyung; Yoon, Hyo Jae Macromolecules, Vol. 51, Issue 11 https://doi.org/10.1021/acs.macromol.8b00550	journal	May 2018
2-Azaallyl Anion Initiated Ring-Opening Polymerization of N -Sulfonyl Aziridines: One-Pot Synthesis of Primary Amine-Ended Telechelic Polyaziridines Wang, Ying; Yang, Ruhan; Luo, Wenyi Macromolecules, Vol. 52, Issue 10 https://doi.org/10.1021/acs.macromol.9b00639	journal	May 2019
Comparison of the Anionic Ring-Opening Polymerizations of N -(Alkylsulfonyl)azetidines Rowe, Elizabeth A.; Reisman, Louis; Jefcoat, Jennifer A. Macromolecules, Vol. 52, Issue 21 https://doi.org/10.1021/acs.macromol.9b01436	journal	October 2019
Competitive Copolymerization: Access to Aziridine Copolymers with Adjustable Gradient Strengths Gleede, Tassilo; Markwart, Jens C.; Huber, Niklas Macromolecules, Vol. 52, Issue 24 https://doi.org/10.1021/acs.macromol.9b01623	journal	December 2019
Carboxylic Acid Initiated Organocatalytic Ring-Opening Polymerization of N-Sulfonyl Aziridines: An Easy Access to Well-Controlled Polyaziridine-Based Architectural and Functionalized Polymers Yang, Ruhan; Wang, Ying; Luo, Wenyi Macromolecules, Vol. 52, Issue 22 https://doi.org/10.1021/acs.macromol.9b01716	journal	November 2019
Multihydroxy Polyamines by Living Anionic Polymerization of Aziridines Rieger, Elisabeth; Manhart, Angelika; Wurm, Frederik R. ACS Macro Letters, Vol. 5, Issue 2 https://doi.org/10.1021/acsmacrolett.5b00901	journal	January 2016
Living Anionic Copolymerization of 1-(Alkylsulfonyl)aziridines to Form Poly(sulfonylaziridine) and Linear Poly(ethylenimine) Reisman, Louis; Mbarushimana, Canisius P.; Cassidy, S. Joel ACS Macro Letters, Vol. 5, Issue 10 https://doi.org/10.1021/acsmacrolett.6b00538	journal	September 2016
Organocatalyzed Anionic Ring-Opening Polymerizations of N -Sulfonyl Aziridines with Organic Superbases Wang, Xin; Liu, Yaya; Li, Zhenjiang ACS Macro Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acsmacrolett.7b00775	journal	November 2017
Microwave-Assisted Desulfonylation of Polysulfonamides toward Polypropylenimine Rieger, Elisabeth; Gleede, Tassilo; Manhart, Angelika ACS Macro Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acsmacrolett.8b00180	journal	May 2018
Linear Well-Defined Polyamines via Anionic Ring-Opening Polymerization of Activated Aziridines: From Mild Desulfonylation to Cell Transfection Gleede, Tassilo; Yu, Fangzhou; Luo, Ying-Li ACS Macro Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acsmacrolett.9b00792	journal	December 2019
Non-Isocyanate and Catalyst-Free Synthesis of a Recyclable Polythiourethane with Cyclic Structure Wu, Shuang; Luo, Ming; Darensbourg, Donald J. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 14 https://doi.org/10.1021/acssuschemeng.0c00435	journal	March 2020
One-Step Photochemical Synthesis of Permanent, Nonleaching, Ultrathin Antimicrobial Coatings for Textiles and Plastics Dhende, Vikram P.; Samanta, Satyabrata; Jones, David M. ACS Applied Materials & Interfaces, Vol. 3, Issue 8 https://doi.org/10.1021/am200324f	journal	June 2011
2-(Trimethylsilyl)ethanesulfonyl (or SES) Group in Amine Protection and Activation Ribière, Patrice; Declerck, Valérie; Martinez, Jean Chemical Reviews, Vol. 106, Issue 6 https://doi.org/10.1021/cr0300587	journal	May 2006
Total Synthesis of the Ramoplanin A2 and Ramoplanose Aglycon Jiang, Wanlong; Wanner, Jutta; Lee, Richard J. Journal of the American Chemical Society, Vol. 125, Issue 7 https://doi.org/10.1021/ja0212314	journal	January 2003
Living Ring-Opening Polymerization of N -Sulfonylaziridines: Synthesis of High Molecular Weight Linear Polyamines Stewart, Ian C.; Lee, Cameron C.; Bergman, Robert G. Journal of the American Chemical Society, Vol. 127, Issue 50 https://doi.org/10.1021/ja0554357	journal	December 2005
The Synthesis of Cyclic Poly(ethylene imine) and Exact Linear Analogues: An Evaluation of Gene Delivery Comparing Polymer Architectures Cortez, Mallory A.; Godbey, W. T.; Fang, Yunlan Journal of the American Chemical Society, Vol. 137, Issue 20 https://doi.org/10.1021/jacs.5b00980	journal	May 2015
Fast Access to Amphiphilic Multiblock Architectures by the Anionic Copolymerization of Aziridines and Ethylene Oxide Gleede, Tassilo; Rieger, Elisabeth; Blankenburg, Jan Journal of the American Chemical Society, Vol. 140, Issue 41 https://doi.org/10.1021/jacs.8b08054	journal	October 2018
Sequential aza-Baylis−Hillman/Ring Closing Metathesis/Aromatization as a Novel Route for the Synthesis of Substituted Pyrroles Declerck, Valérie; Ribière, Patrice; Martinez, Jean The Journal of Organic Chemistry, Vol. 69, Issue 24 https://doi.org/10.1021/jo048519r	journal	November 2004
Synthesis of Amine- and Thiol-Modified Nucleoside Phosphoramidites for Site-Specific Introduction of Biophysical Probes into RNA Jin, Shengxi; Miduturu, Chandrasekhar V.; McKinney, David C. The Journal of Organic Chemistry, Vol. 70, Issue 11 https://doi.org/10.1021/jo050061l	journal	April 2005
2-Trimethylsilylethanesulfonyl (SES) versus Tosyl (Ts) Protecting Group in the Preparation of Nitrogen-Containing Five-Membered Rings. A Novel Route for the Synthesis of Substituted Pyrrolines and Pyrrolidines Declerck, Valérie; Allouchi, Hassan; Martinez, Jean The Journal of Organic Chemistry, Vol. 72, Issue 4 https://doi.org/10.1021/jo062239p	journal	January 2007
Total Synthesis of Proposed Auranthine Kshirsagar, Umesh A.; Puranik, Vedavati G.; Argade, Narshinha P. The Journal of Organic Chemistry, Vol. 75, Issue 8 https://doi.org/10.1021/jo100400z	journal	March 2010
PhINSes: A New Iminoiodinane Reagent for the Copper-Catalyzed Aziridination of Olefins Dauban, Philippe; Dodd, Robert H. The Journal of Organic Chemistry, Vol. 64, Issue 14 https://doi.org/10.1021/jo990356x	journal	June 1999
Development of a Stepwise [3 + 3] Annelation to Functionalized Piperidines Goodenough, Katharine M.; Raubo, Piotr; Harrity, Joseph P. A. Organic Letters, Vol. 7, Issue 14 https://doi.org/10.1021/ol050965t	journal	June 2005
Proteome-derived, database-searchable peptide libraries for identifying protease cleavage sites Schilling, Oliver; Overall, Christopher M. Nature Biotechnology, Vol. 26, Issue 6 https://doi.org/10.1038/nbt1408	journal	May 2008
Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization Xu, Jiaxi; Wang, Xin; Hadjichristidis, Nikos Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-27377-3	journal	December 2021
N-Ferrocenylsulfonyl-2-methylaziridine: the first ferrocene monomer for the anionic (co)polymerization of aziridines Homann-Müller, Tatjana; Rieger, Elisabeth; Alkan, Arda Polymer Chemistry, Vol. 7, Issue 35 https://doi.org/10.1039/C6PY01019A	journal	January 2016
The living anionic polymerization of activated aziridines: a systematic study of reaction conditions and kinetics Rieger, Elisabeth; Gleede, Tassilo; Weber, Katja Polymer Chemistry, Vol. 8, Issue 18 https://doi.org/10.1039/C7PY00436B	journal	January 2017
Aziridines and azetidines: building blocks for polyamines by anionic and cationic ring-opening polymerization Gleede, Tassilo; Reisman, Louis; Rieger, Elisabeth Polymer Chemistry, Vol. 10, Issue 24 https://doi.org/10.1039/C9PY00278B	journal	January 2019
Solvent and catalyst-free modification of hyperbranched polyethyleneimines by ring-opening-addition or ring-opening-polymerization of N-sulfonyl aziridines Li, Zhunxuan; Chen, Rui; Wang, Ying Polymer Chemistry, Vol. 12, Issue 12 https://doi.org/10.1039/D1PY00125F	journal	January 2021

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Polymerizations of 2-(Trimethylsilyl)ethanesulfonyl-activated aziridines

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