Inversion of Diaza[5]Helicenes Through an N−N Bond Breaking Pathway
1,1’,10,10’‐Biphenothiazine and its S,S,S’,S’‐tetroxide are diaza[5]helicenes with N−N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N−N bond breaking pathway rather than the general conformational pathway. In these diaz...
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| Veröffentlicht in: | Chemistry : a European journal 2023-08, Vol.29 (43), p.e202301466-n/a |
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| creator | Kobayashi, Toshifumi Ishiwari, Fumitaka Fukushima, Takanori Nojima, Yuki Hasegawa, Masashi Mazaki, Yasuhiro Hanaya, Kengo Sugai, Takeshi Higashibayashi, Shuhei |
| description | 1,1’,10,10’‐Biphenothiazine and its S,S,S’,S’‐tetroxide are diaza[5]helicenes with N−N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N−N bond breaking pathway rather than the general conformational pathway. In these diaza[5]helicenes with this inversion mechanism, the reduction of electronic repulsion in the N−N bond by modification of S to SO2 at the outer position of the helix led to a significantly higher inversion barrier, 35.3 kcal/mol, compared to [5]helicene. 1,1’,10,10’‐Biphenothiazine S,S,S’,S’‐tetroxide was highly resistant to acid‐mediated N−N bond breaking and racemization under acidic conditions.
Diaza[5]helicenes with N−N linkages were found to racemize through the N−N bond‐breaking pathway by kinetic experiments and DFT calculations. Modification of S to SO2 at the outer position of the helix reduced the electronic repulsion in the N−N bond, resulting in a significant increase in the inversion barrier. |
| doi_str_mv | 10.1002/chem.202301466 |
| format | Article |
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Diaza[5]helicenes with N−N linkages were found to racemize through the N−N bond‐breaking pathway by kinetic experiments and DFT calculations. Modification of S to SO2 at the outer position of the helix reduced the electronic repulsion in the N−N bond, resulting in a significant increase in the inversion barrier.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202301466</identifier><identifier>PMID: 37194616</identifier><language>eng</language><publisher>Germany</publisher><subject>axis chirality ; bond breaking ; heterohelicene ; inversion ; racemization</subject><ispartof>Chemistry : a European journal, 2023-08, Vol.29 (43), p.e202301466-n/a</ispartof><rights>2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH</rights><rights>2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c3406-c0b4043c6e2fbb167e6f716b1f689780a6285828945bf72424dfe0b074c25d9b3</cites><orcidid>0000-0002-0200-4510 ; 0000-0003-3302-6496 ; 0000-0002-9152-5966 ; 0000-0003-4416-6435 ; 0000-0002-2957-461X ; 0000-0001-5586-9238</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.202301466$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202301466$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37194616$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kobayashi, Toshifumi</creatorcontrib><creatorcontrib>Ishiwari, Fumitaka</creatorcontrib><creatorcontrib>Fukushima, Takanori</creatorcontrib><creatorcontrib>Nojima, Yuki</creatorcontrib><creatorcontrib>Hasegawa, Masashi</creatorcontrib><creatorcontrib>Mazaki, Yasuhiro</creatorcontrib><creatorcontrib>Hanaya, Kengo</creatorcontrib><creatorcontrib>Sugai, Takeshi</creatorcontrib><creatorcontrib>Higashibayashi, Shuhei</creatorcontrib><title>Inversion of Diaza[5]Helicenes Through an N−N Bond Breaking Pathway</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>1,1’,10,10’‐Biphenothiazine and its S,S,S’,S’‐tetroxide are diaza[5]helicenes with N−N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N−N bond breaking pathway rather than the general conformational pathway. In these diaza[5]helicenes with this inversion mechanism, the reduction of electronic repulsion in the N−N bond by modification of S to SO2 at the outer position of the helix led to a significantly higher inversion barrier, 35.3 kcal/mol, compared to [5]helicene. 1,1’,10,10’‐Biphenothiazine S,S,S’,S’‐tetroxide was highly resistant to acid‐mediated N−N bond breaking and racemization under acidic conditions.
Diaza[5]helicenes with N−N linkages were found to racemize through the N−N bond‐breaking pathway by kinetic experiments and DFT calculations. Modification of S to SO2 at the outer position of the helix reduced the electronic repulsion in the N−N bond, resulting in a significant increase in the inversion barrier.</description><subject>axis chirality</subject><subject>bond breaking</subject><subject>heterohelicene</subject><subject>inversion</subject><subject>racemization</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><recordid>eNqFkM1OwkAURidGI4huXZpZuinOX6edpSAKCaILXBnTTNs7tFpanaESfALXPqJPYgmIS5Ob3M35zuIgdEpJlxLCLpIM5l1GGCdUSLmH2tRn1OOB9PdRmygReNLnqoWOnHsmhCjJ-SFq8YAqIalso8GofAfr8qrElcFXuf7Qj_7TEIo8gRIcnma2qmcZ1iWefH9-TXCvKlPcs6Bf8nKG7_UiW-rVMTowunBwsv0d9HA9mPaH3vjuZtS_HHsJF0R6CYkFETyRwEwcUxmANAGVMTUyVEFItGShH7JQCT82ARNMpAZITAKRMD9VMe-g84331VZvNbhFNM9dAkWhS6hqF7GQiuaUZA3a3aCJrZyzYKJXm8-1XUWUROt00TpdtEvXDM627jqeQ7rDf1s1gNoAy7yA1T-6qD8c3P7JfwCGJXmn</recordid><startdate>20230801</startdate><enddate>20230801</enddate><creator>Kobayashi, Toshifumi</creator><creator>Ishiwari, Fumitaka</creator><creator>Fukushima, Takanori</creator><creator>Nojima, Yuki</creator><creator>Hasegawa, Masashi</creator><creator>Mazaki, Yasuhiro</creator><creator>Hanaya, Kengo</creator><creator>Sugai, Takeshi</creator><creator>Higashibayashi, Shuhei</creator><scope>24P</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-0200-4510</orcidid><orcidid>https://orcid.org/0000-0003-3302-6496</orcidid><orcidid>https://orcid.org/0000-0002-9152-5966</orcidid><orcidid>https://orcid.org/0000-0003-4416-6435</orcidid><orcidid>https://orcid.org/0000-0002-2957-461X</orcidid><orcidid>https://orcid.org/0000-0001-5586-9238</orcidid></search><sort><creationdate>20230801</creationdate><title>Inversion of Diaza[5]Helicenes Through an N−N Bond Breaking Pathway</title><author>Kobayashi, Toshifumi ; Ishiwari, Fumitaka ; Fukushima, Takanori ; Nojima, Yuki ; Hasegawa, Masashi ; Mazaki, Yasuhiro ; Hanaya, Kengo ; Sugai, Takeshi ; Higashibayashi, Shuhei</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3406-c0b4043c6e2fbb167e6f716b1f689780a6285828945bf72424dfe0b074c25d9b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>axis chirality</topic><topic>bond breaking</topic><topic>heterohelicene</topic><topic>inversion</topic><topic>racemization</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kobayashi, Toshifumi</creatorcontrib><creatorcontrib>Ishiwari, Fumitaka</creatorcontrib><creatorcontrib>Fukushima, Takanori</creatorcontrib><creatorcontrib>Nojima, Yuki</creatorcontrib><creatorcontrib>Hasegawa, Masashi</creatorcontrib><creatorcontrib>Mazaki, Yasuhiro</creatorcontrib><creatorcontrib>Hanaya, Kengo</creatorcontrib><creatorcontrib>Sugai, Takeshi</creatorcontrib><creatorcontrib>Higashibayashi, Shuhei</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kobayashi, Toshifumi</au><au>Ishiwari, Fumitaka</au><au>Fukushima, Takanori</au><au>Nojima, Yuki</au><au>Hasegawa, Masashi</au><au>Mazaki, Yasuhiro</au><au>Hanaya, Kengo</au><au>Sugai, Takeshi</au><au>Higashibayashi, Shuhei</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Inversion of Diaza[5]Helicenes Through an N−N Bond Breaking Pathway</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2023-08-01</date><risdate>2023</risdate><volume>29</volume><issue>43</issue><spage>e202301466</spage><epage>n/a</epage><pages>e202301466-n/a</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>1,1’,10,10’‐Biphenothiazine and its S,S,S’,S’‐tetroxide are diaza[5]helicenes with N−N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N−N bond breaking pathway rather than the general conformational pathway. In these diaza[5]helicenes with this inversion mechanism, the reduction of electronic repulsion in the N−N bond by modification of S to SO2 at the outer position of the helix led to a significantly higher inversion barrier, 35.3 kcal/mol, compared to [5]helicene. 1,1’,10,10’‐Biphenothiazine S,S,S’,S’‐tetroxide was highly resistant to acid‐mediated N−N bond breaking and racemization under acidic conditions.
Diaza[5]helicenes with N−N linkages were found to racemize through the N−N bond‐breaking pathway by kinetic experiments and DFT calculations. Modification of S to SO2 at the outer position of the helix reduced the electronic repulsion in the N−N bond, resulting in a significant increase in the inversion barrier.</abstract><cop>Germany</cop><pmid>37194616</pmid><doi>10.1002/chem.202301466</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-0200-4510</orcidid><orcidid>https://orcid.org/0000-0003-3302-6496</orcidid><orcidid>https://orcid.org/0000-0002-9152-5966</orcidid><orcidid>https://orcid.org/0000-0003-4416-6435</orcidid><orcidid>https://orcid.org/0000-0002-2957-461X</orcidid><orcidid>https://orcid.org/0000-0001-5586-9238</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | axis chirality bond breaking heterohelicene inversion racemization |
| title | Inversion of Diaza[5]Helicenes Through an N−N Bond Breaking Pathway |
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