The postpolymerization modification of polymers produced by living polymerization is an attractive method to create precision nanomaterials. We describe the living cationic ring-opening polymerization of a 2-alkylthio-2-oxazoline to furnish a polythiocarbamate. The polythiocarbamate is activated toward substitution by - and -nucleophiles via oxidation of the S to an SO. Mild substitution conditions provide broad functional group tolerance, constituting a versatile postpolymerization modification platform with access to a diversity of polyureas and polythiocarbamates. We further demonstrate the utility of this strategy by synthesizing and functionalizing block copolymers.
Science. 1974 May 3;184(4136):573-4
[PMID:
4821957]
Chem Res Toxicol. 2004 Feb;17(2):258-67
[PMID:
14967014]
Macromol Rapid Commun. 2011 Sep 15;32(18):1419-41
[PMID:
21714027]
Angew Chem Int Ed Engl. 2018 Nov 19;57(47):15400-15404
[PMID:
30303605]
Bioconjug Chem. 2014 Apr 16;25(4):629-39
[PMID:
24641212]
Chem Res Toxicol. 2000 Apr;13(4):237-44
[PMID:
10775322]
Macromol Rapid Commun. 2019 Jan;40(1):e1800590
[PMID:
30368966]
ACS Cent Sci. 2019 May 22;5(5):789-795
[PMID:
31139715]
ACS Macro Lett. 2018 Jan 16;7(1):122-126
[PMID:
35610928]
Biomaterials. 2018 Sep;178:204-280
[PMID:
29945064]
Chem Commun (Camb). 2015 Apr 28;51(33):7116-9
[PMID:
25811298]
Angew Chem Int Ed Engl. 2009;48(1):48-58
[PMID:
19040233]
Chem Sci. 2019 Feb 27;10(14):3994-4003
[PMID:
31015940]
J Org Chem. 2005 Aug 19;70(17):6960-3
[PMID:
16095326]
Angew Chem Int Ed Engl. 2007;46(40):7621-4
[PMID:
17768748]
Proc Natl Acad Sci U S A. 2015 Jul 7;112(27):8260-5
[PMID:
26100900]
Nat Commun. 2015 Dec 14;6:8929
[PMID:
26656447]
J Am Chem Soc. 2018 Sep 26;140(38):11911-11915
[PMID:
30215257]
