Stereoselective oxidation of phenoxathiin-based thiacalix[4]arenes - stereomutation of sulfoxide groups
A phenoxathiin-based macrocycle represents an inherently chiral building block, well accessible in two steps from the starting thiacalix[4]arene. The oxidized derivatives bearing one sulfoxide group and three sulfonyl groups were found to exhibit unexpected stereochemical preferences of the sulfoxid...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2023-06, Vol.21 (22), p.462-463 |
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| container_title | Organic & biomolecular chemistry |
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| creator | Broftová, N Landovský, T Dvo áková, H Eigner, V Krupi ka, M Lhoták, P |
| description | A phenoxathiin-based macrocycle represents an inherently chiral building block, well accessible in two steps from the starting thiacalix[4]arene. The oxidized derivatives bearing one sulfoxide group and three sulfonyl groups were found to exhibit unexpected stereochemical preferences of the sulfoxide group during transformations. The sulfoxide moiety is always pointing out of the cavity (S&z.dbd;O
out
), while the opposite (S&z.dbd;O
in
) configuration was never obtained by direct oxidation. In order to achieve full oxidation to sulfone, the configuration of the sulfoxide group must first be changed by a photochemical inversion before the final oxidation occurs. The phenomenon of stereomutation of the sulfoxide group in the thiacalixarene series was studied using a combination of experimental (NMR and single crystal X-ray analysis) and theoretical (DFT) approaches.
Phenoxathiin-based thiacalix[4]arene possessing an "-SO-
out
" configuration must be changed to an "
in
" isomer before its subsequent transformation to the corresponding sulfone. |
| doi_str_mv | 10.1039/d3ob00530e |
| format | Article |
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out
), while the opposite (S&z.dbd;O
in
) configuration was never obtained by direct oxidation. In order to achieve full oxidation to sulfone, the configuration of the sulfoxide group must first be changed by a photochemical inversion before the final oxidation occurs. The phenomenon of stereomutation of the sulfoxide group in the thiacalixarene series was studied using a combination of experimental (NMR and single crystal X-ray analysis) and theoretical (DFT) approaches.
Phenoxathiin-based thiacalix[4]arene possessing an "-SO-
out
" configuration must be changed to an "
in
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out
), while the opposite (S&z.dbd;O
in
) configuration was never obtained by direct oxidation. In order to achieve full oxidation to sulfone, the configuration of the sulfoxide group must first be changed by a photochemical inversion before the final oxidation occurs. The phenomenon of stereomutation of the sulfoxide group in the thiacalixarene series was studied using a combination of experimental (NMR and single crystal X-ray analysis) and theoretical (DFT) approaches.
Phenoxathiin-based thiacalix[4]arene possessing an "-SO-
out
" configuration must be changed to an "
in
" isomer before its subsequent transformation to the corresponding sulfone.</description><subject>Aromatic compounds</subject><subject>Configurations</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Oxidation</subject><subject>Photochemicals</subject><subject>Single crystals</subject><subject>Stereoselectivity</subject><subject>Sulfoxides</subject><subject>X ray analysis</subject><issn>1477-0520</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNpdkctLw0AQxhdRtFYv3pWAFxGi-0iy2aPW-oBCD-pJJGx2Z2tKmq27idT_3u3DCp7m9ZuP4RuETgi-IpiJa81siXHKMOygHkk4j0Mhdrc5xQfo0PspxkTwLNlHB4xTktM866HJcwsOrIcaVFt9QWQXlZZtZZvImmj-AY1dyPajqpq4lB50FHKpZF0t3pJ36aABH8WRX4nMuna76bvaLKUgmjjbzf0R2jOy9nC8iX30ej98GTzGo_HD0-BmFCvGWRtrQ5VK0pxKxZROKdUZybRMMkJLLoGGLi9znnKTZwklmqbSSC1UykDk2hjWRxdr3bmznx34tphVXkFdywZs5wuakxynXCQ8oOf_0KntXBOuCxSlQmSCpIG6XFPKWe8dmGLuqpl03wXBxdL-4o6Nb1f2DwN8tpHsyhnoLfrrdwBO14Dzajv9-x_7ATHmi7k</recordid><startdate>20230607</startdate><enddate>20230607</enddate><creator>Broftová, N</creator><creator>Landovský, T</creator><creator>Dvo áková, H</creator><creator>Eigner, V</creator><creator>Krupi ka, M</creator><creator>Lhoták, P</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QO</scope><scope>7T7</scope><scope>7TM</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>P64</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-1014-3980</orcidid><orcidid>https://orcid.org/0000-0003-0694-4128</orcidid><orcidid>https://orcid.org/0000-0003-3617-6596</orcidid></search><sort><creationdate>20230607</creationdate><title>Stereoselective oxidation of phenoxathiin-based thiacalix[4]arenes - stereomutation of sulfoxide groups</title><author>Broftová, N ; Landovský, T ; Dvo áková, H ; Eigner, V ; Krupi ka, M ; Lhoták, P</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c373t-df2cc4582ac3cd522d616da4612b7ae2c3c7b8757f86421d25afad9c53e98dff3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Aromatic compounds</topic><topic>Configurations</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Oxidation</topic><topic>Photochemicals</topic><topic>Single crystals</topic><topic>Stereoselectivity</topic><topic>Sulfoxides</topic><topic>X ray analysis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Broftová, N</creatorcontrib><creatorcontrib>Landovský, T</creatorcontrib><creatorcontrib>Dvo áková, H</creatorcontrib><creatorcontrib>Eigner, V</creatorcontrib><creatorcontrib>Krupi ka, M</creatorcontrib><creatorcontrib>Lhoták, P</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Biotechnology Research Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Nucleic Acids Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Organic & biomolecular chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Broftová, N</au><au>Landovský, T</au><au>Dvo áková, H</au><au>Eigner, V</au><au>Krupi ka, M</au><au>Lhoták, P</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Stereoselective oxidation of phenoxathiin-based thiacalix[4]arenes - stereomutation of sulfoxide groups</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2023-06-07</date><risdate>2023</risdate><volume>21</volume><issue>22</issue><spage>462</spage><epage>463</epage><pages>462-463</pages><issn>1477-0520</issn><eissn>1477-0539</eissn><abstract>A phenoxathiin-based macrocycle represents an inherently chiral building block, well accessible in two steps from the starting thiacalix[4]arene. The oxidized derivatives bearing one sulfoxide group and three sulfonyl groups were found to exhibit unexpected stereochemical preferences of the sulfoxide group during transformations. The sulfoxide moiety is always pointing out of the cavity (S&z.dbd;O
out
), while the opposite (S&z.dbd;O
in
) configuration was never obtained by direct oxidation. In order to achieve full oxidation to sulfone, the configuration of the sulfoxide group must first be changed by a photochemical inversion before the final oxidation occurs. The phenomenon of stereomutation of the sulfoxide group in the thiacalixarene series was studied using a combination of experimental (NMR and single crystal X-ray analysis) and theoretical (DFT) approaches.
Phenoxathiin-based thiacalix[4]arene possessing an "-SO-
out
" configuration must be changed to an "
in
" isomer before its subsequent transformation to the corresponding sulfone.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>37218286</pmid><doi>10.1039/d3ob00530e</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0003-1014-3980</orcidid><orcidid>https://orcid.org/0000-0003-0694-4128</orcidid><orcidid>https://orcid.org/0000-0003-3617-6596</orcidid><oa>free_for_read</oa></addata></record> |
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| ispartof | Organic & biomolecular chemistry, 2023-06, Vol.21 (22), p.462-463 |
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| language | eng |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Aromatic compounds Configurations NMR Nuclear magnetic resonance Oxidation Photochemicals Single crystals Stereoselectivity Sulfoxides X ray analysis |
| title | Stereoselective oxidation of phenoxathiin-based thiacalix[4]arenes - stereomutation of sulfoxide groups |
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