Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis
Hypervalent iodine λ[superscript 3]-benziodoxoles are common electrophilic transfer reagents known for their enhanced stability compared to their non-cyclic analogues. Herein we present data showing that chlorobenziodoxole reacts with two different thiolate nucleophiles (thiocyanate and trifluoromet...
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| Format: | Article |
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Wiley Blackwell
2015
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| Online Access: | http://hdl.handle.net/1721.1/99674 https://orcid.org/0000-0003-3875-4775 |
| _version_ | 1826204830334451712 |
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| author | Vinogradova, Ekaterina V. Mueller, Peter Buchwald, Stephen Leffler |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Vinogradova, Ekaterina V. Mueller, Peter Buchwald, Stephen Leffler |
| author_sort | Vinogradova, Ekaterina V. |
| collection | MIT |
| description | Hypervalent iodine λ[superscript 3]-benziodoxoles are common electrophilic transfer reagents known for their enhanced stability compared to their non-cyclic analogues. Herein we present data showing that chlorobenziodoxole reacts with two different thiolate nucleophiles (thiocyanate and trifluoromethylthiolate), resulting in the formation of stable thioperoxy complexes rather than the expected benziodoxole derivatives. We further report a revised structure for the earlier described electrophilic trifluoromethylthiolation reagent (1), which was previously believed to contain the benziodoxole framework. Our findings, which are based on a combination of analytical techniques, including the recently introduced crystalline sponge method for X-ray analysis, unambiguously demonstrate that 1 is a thioperoxy compound both in solution and the solid state. |
| first_indexed | 2024-09-23T13:01:45Z |
| format | Article |
| id | mit-1721.1/99674 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:01:45Z |
| publishDate | 2015 |
| publisher | Wiley Blackwell |
| record_format | dspace |
| spelling | mit-1721.1/996742022-10-01T12:37:20Z Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis Vinogradova, Ekaterina V. Mueller, Peter Buchwald, Stephen Leffler Massachusetts Institute of Technology. Department of Chemistry Vinogradova, Ekaterina V. Mueller, Peter Buchwald, Stephen Leffler Hypervalent iodine λ[superscript 3]-benziodoxoles are common electrophilic transfer reagents known for their enhanced stability compared to their non-cyclic analogues. Herein we present data showing that chlorobenziodoxole reacts with two different thiolate nucleophiles (thiocyanate and trifluoromethylthiolate), resulting in the formation of stable thioperoxy complexes rather than the expected benziodoxole derivatives. We further report a revised structure for the earlier described electrophilic trifluoromethylthiolation reagent (1), which was previously believed to contain the benziodoxole framework. Our findings, which are based on a combination of analytical techniques, including the recently introduced crystalline sponge method for X-ray analysis, unambiguously demonstrate that 1 is a thioperoxy compound both in solution and the solid state. National Institutes of Health (U.S.) (Award GM58160) 2015-11-03T13:02:06Z 2015-11-03T13:02:06Z 2014-02 2013-12 Article http://purl.org/eprint/type/JournalArticle 14337851 1521-3773 http://hdl.handle.net/1721.1/99674 Vinogradova, Ekaterina V., Peter Muller, and Stephen L. Buchwald. “Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-Ray Analysis.” Angew. Chem. Int. Ed. 53, no. 12 (February 14, 2014): 3125–3128. https://orcid.org/0000-0003-3875-4775 en_US http://dx.doi.org/10.1002/anie.201310897 Angewandte Chemie International Edition Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley Blackwell PMC |
| spellingShingle | Vinogradova, Ekaterina V. Mueller, Peter Buchwald, Stephen Leffler Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis |
| title | Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis |
| title_full | Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis |
| title_fullStr | Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis |
| title_full_unstemmed | Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis |
| title_short | Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis |
| title_sort | structural reevaluation of the electrophilic hypervalent iodine reagent for trifluoromethylthiolation supported by the crystalline sponge method for x ray analysis |
| url | http://hdl.handle.net/1721.1/99674 https://orcid.org/0000-0003-3875-4775 |
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