Cargando…
Unsymmetrical polysulfidation via designed bilateral disulfurating reagents
Sulfur-sulfur motifs widely occur in vital function and drug design, which yearns for polysulfide construction in an efficient manner. However, it is a great challenge to install desired functional groups on both sides of sulfur-sulfur bonds at liberty. Herein, we designed a mesocyclic bilateral dis...
Autores principales: | , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7441163/ https://www.ncbi.nlm.nih.gov/pubmed/32820174 http://dx.doi.org/10.1038/s41467-020-18029-z |
_version_ | 1783573250942435328 |
---|---|
author | Xue, Jiahui Jiang, Xuefeng |
author_facet | Xue, Jiahui Jiang, Xuefeng |
author_sort | Xue, Jiahui |
collection | PubMed |
description | Sulfur-sulfur motifs widely occur in vital function and drug design, which yearns for polysulfide construction in an efficient manner. However, it is a great challenge to install desired functional groups on both sides of sulfur-sulfur bonds at liberty. Herein, we designed a mesocyclic bilateral disulfurating reagent for sequential assembly and modular installation of polysulfides. Based on S-O bond dissociation energy imparity (mesocyclic compared to linear imparity is at least 5.34 kcal mol(−1) higher), diverse types of functional molecules can be bridged via sulfur-sulfur bonds distinctly. With these stable reagents, excellent reactivities with nucleophiles including C, N and S are comprehensively demonstrated, sequentially installing on both sides of sulfur-sulfur motif with various substituents to afford six species of unsymmetrical polysulfides including di-, tri- and even tetra-sulfides. Life-related molecules, natural products and pharmaceuticals can be successively cross-linked with sulfur-sulfur bond. Remarkably, the cyclization of tri- and tetra-peptides affords 15- and 18-membered cyclic disulfide peptides with this reagent, respectively. |
format | Online Article Text |
id | pubmed-7441163 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-74411632020-09-02 Unsymmetrical polysulfidation via designed bilateral disulfurating reagents Xue, Jiahui Jiang, Xuefeng Nat Commun Article Sulfur-sulfur motifs widely occur in vital function and drug design, which yearns for polysulfide construction in an efficient manner. However, it is a great challenge to install desired functional groups on both sides of sulfur-sulfur bonds at liberty. Herein, we designed a mesocyclic bilateral disulfurating reagent for sequential assembly and modular installation of polysulfides. Based on S-O bond dissociation energy imparity (mesocyclic compared to linear imparity is at least 5.34 kcal mol(−1) higher), diverse types of functional molecules can be bridged via sulfur-sulfur bonds distinctly. With these stable reagents, excellent reactivities with nucleophiles including C, N and S are comprehensively demonstrated, sequentially installing on both sides of sulfur-sulfur motif with various substituents to afford six species of unsymmetrical polysulfides including di-, tri- and even tetra-sulfides. Life-related molecules, natural products and pharmaceuticals can be successively cross-linked with sulfur-sulfur bond. Remarkably, the cyclization of tri- and tetra-peptides affords 15- and 18-membered cyclic disulfide peptides with this reagent, respectively. Nature Publishing Group UK 2020-08-20 /pmc/articles/PMC7441163/ /pubmed/32820174 http://dx.doi.org/10.1038/s41467-020-18029-z Text en © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Xue, Jiahui Jiang, Xuefeng Unsymmetrical polysulfidation via designed bilateral disulfurating reagents |
title | Unsymmetrical polysulfidation via designed bilateral disulfurating reagents |
title_full | Unsymmetrical polysulfidation via designed bilateral disulfurating reagents |
title_fullStr | Unsymmetrical polysulfidation via designed bilateral disulfurating reagents |
title_full_unstemmed | Unsymmetrical polysulfidation via designed bilateral disulfurating reagents |
title_short | Unsymmetrical polysulfidation via designed bilateral disulfurating reagents |
title_sort | unsymmetrical polysulfidation via designed bilateral disulfurating reagents |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7441163/ https://www.ncbi.nlm.nih.gov/pubmed/32820174 http://dx.doi.org/10.1038/s41467-020-18029-z |
work_keys_str_mv | AT xuejiahui unsymmetricalpolysulfidationviadesignedbilateraldisulfuratingreagents AT jiangxuefeng unsymmetricalpolysulfidationviadesignedbilateraldisulfuratingreagents |