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      Dithioesters: simple, tunable, cysteine-selective H 2S donors†

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          Abstract

          Dithioesters release H 2S upon treatment with cysteine, and the rate can be tuned by structural and electronic modifications.

          Abstract

          Dithioesters have a rich history in polymer chemistry for RAFT polymerizations and are readily accessible through different synthetic methods. Here we demonstrate that the dithioester functional group is a tunable motif that releases H 2S upon reaction with cysteine and that structural and electronic modifications enable the rate of cysteine-mediated H 2S release to be modified. In addition, we use (bis)phenyl dithioester to carry out kinetic and mechanistic investigations, which demonstrate that the initial attack by cysteine is the rate-limiting step of the reaction. These insights are further supported by complementary DFT calculations. We anticipate that the results from these investigations will allow for the further development of dithioesters as important chemical motifs for studying H 2S chemical biology.

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          Author and article information

          Journal
          Chem Sci
          Chem Sci
          Chemical Science
          Royal Society of Chemistry
          2041-6520
          2041-6539
          30 November 2018
          14 February 2019
          : 10
          : 6
          : 1773-1779
          Affiliations
          [a ] Department of Chemistry and Biochemistry , Materials Science Institute , Institute of Molecular Biology , University of Oregon , Eugene , Oregon 97403 , USA . Email: pluth@ 123456uoregon.edu
          Author information
          http://orcid.org/0000-0003-1250-9480
          http://orcid.org/0000-0002-7132-768X
          http://orcid.org/0000-0003-3604-653X
          Article
          c8sc04683b
          10.1039/c8sc04683b
          6368244
          9ef3181f-8e4c-4268-9da3-9e87c61fa0e9
          This journal is © The Royal Society of Chemistry 2019

          This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)

          History
          : 20 October 2018
          : 30 November 2018
          Categories
          Chemistry

          Notes

          †Electronic supplementary information (ESI) available: Experimental details, spectra, computational details, tabulated geometries. See DOI: 10.1039/c8sc04683b


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