Chemical transformations of push-pull fluorenones: push-pull dibenzodicyanofulvenes as well as fluorenone- and dibenzodicyanofulvene-tetracyanobutadiene conjugates
Push-pull fluorenones (FOs) were synthesized by treating a benzopentalenequinone (BPO) derivative with alkynes that bear an electron-rich aniline moiety via a regioselective [4 + 2] cycloaddition (CA) followed by a [4 + 1] retrocycloaddition (RCA). The resulting FOs were readily converted into diben...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2020-06, Vol.18 (22), p.4198-429 |
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| creator | Kato, Shin-ichiro Kijima, Tomokazu Shiota, Yoshihito Abe, Tsukasa Kuwako, Satoshi Miyauchi, Hidenori Yoshikawa, Naoki Yamamoto, Koji Yoshizawa, Kazunari Yoshihara, Toshitada Tobita, Seiji Nakamura, Yosuke |
| description | Push-pull fluorenones (FOs) were synthesized by treating a benzopentalenequinone (BPO) derivative with alkynes that bear an electron-rich aniline moiety
via
a regioselective [4 + 2] cycloaddition (CA) followed by a [4 + 1] retrocycloaddition (RCA). The resulting FOs were readily converted into dibenzodicyanofulvenes (DBDCFs) by treatment with malononitrile in the presence of TiCl
4
and pyridine. The FOs and DBDCFs exhibit intramolecular charge-transfer (ICT) that manifests in absorptions at 350-650 nm and amphoteric electrochemical behavior. Furthermore, FOs and DBDCFs that contain a C&z.tbd;C bond react with tetracyanoethylene in a formal [2 + 2] CA followed by a retro-electrocyclization to afford sterically congested tetracyanobutadiene (TCBD) conjugates. The substituent (H or Me) on the aromatic ring adjacent to the butadiene moiety thereby determines whether the butadiene adopts an s-
cis
or s-
trans
conformation, and thus controls the physicochemical properties of the resulting TCBDs. The TCBD conjugates exhibit ICT absorptions (≤800 nm) together with up to four reversible reduction steps.
We report push-pull fluorenones (FOs) that can be transformed into dibenzodicyanofulvenes (DBDCFs). These FOs and DBDCFs, which contain a C&z.tbd;C bond, can subsequently be converted into tetracyanobutadiene conjugates. |
| doi_str_mv | 10.1039/c9ob02706h |
| format | Article |
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via
a regioselective [4 + 2] cycloaddition (CA) followed by a [4 + 1] retrocycloaddition (RCA). The resulting FOs were readily converted into dibenzodicyanofulvenes (DBDCFs) by treatment with malononitrile in the presence of TiCl
4
and pyridine. The FOs and DBDCFs exhibit intramolecular charge-transfer (ICT) that manifests in absorptions at 350-650 nm and amphoteric electrochemical behavior. Furthermore, FOs and DBDCFs that contain a C&z.tbd;C bond react with tetracyanoethylene in a formal [2 + 2] CA followed by a retro-electrocyclization to afford sterically congested tetracyanobutadiene (TCBD) conjugates. The substituent (H or Me) on the aromatic ring adjacent to the butadiene moiety thereby determines whether the butadiene adopts an s-
cis
or s-
trans
conformation, and thus controls the physicochemical properties of the resulting TCBDs. The TCBD conjugates exhibit ICT absorptions (≤800 nm) together with up to four reversible reduction steps.
We report push-pull fluorenones (FOs) that can be transformed into dibenzodicyanofulvenes (DBDCFs). These FOs and DBDCFs, which contain a C&z.tbd;C bond, can subsequently be converted into tetracyanobutadiene conjugates.</description><identifier>ISSN: 1477-0520</identifier><identifier>EISSN: 1477-0539</identifier><identifier>DOI: 10.1039/c9ob02706h</identifier><identifier>PMID: 32191251</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Alkynes ; Aniline ; Aromatic compounds ; Butadiene ; Charge transfer ; Conformation ; Conjugates ; Crystallography ; Cycloaddition ; Electrochemical analysis ; Electrochemistry ; Malononitrile ; NMR ; Nuclear magnetic resonance ; Physicochemical properties ; Pyridines ; Retirement</subject><ispartof>Organic & biomolecular chemistry, 2020-06, Vol.18 (22), p.4198-429</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c429t-17b185a28a86f365a6abedb238c7bdc4f65e4dc9658c089fd10ca0cc5663f683</citedby><cites>FETCH-LOGICAL-c429t-17b185a28a86f365a6abedb238c7bdc4f65e4dc9658c089fd10ca0cc5663f683</cites><orcidid>0000-0003-0866-3207 ; 0000-0002-7960-0740 ; 0000-0002-6047-1336 ; 0000-0003-2054-9845 ; 0000-0002-6279-9722 ; 0000-0001-8024-7318 ; 0000-0001-5310-0062</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27915,27916</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/32191251$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kato, Shin-ichiro</creatorcontrib><creatorcontrib>Kijima, Tomokazu</creatorcontrib><creatorcontrib>Shiota, Yoshihito</creatorcontrib><creatorcontrib>Abe, Tsukasa</creatorcontrib><creatorcontrib>Kuwako, Satoshi</creatorcontrib><creatorcontrib>Miyauchi, Hidenori</creatorcontrib><creatorcontrib>Yoshikawa, Naoki</creatorcontrib><creatorcontrib>Yamamoto, Koji</creatorcontrib><creatorcontrib>Yoshizawa, Kazunari</creatorcontrib><creatorcontrib>Yoshihara, Toshitada</creatorcontrib><creatorcontrib>Tobita, Seiji</creatorcontrib><creatorcontrib>Nakamura, Yosuke</creatorcontrib><title>Chemical transformations of push-pull fluorenones: push-pull dibenzodicyanofulvenes as well as fluorenone- and dibenzodicyanofulvene-tetracyanobutadiene conjugates</title><title>Organic & biomolecular chemistry</title><addtitle>Org Biomol Chem</addtitle><description>Push-pull fluorenones (FOs) were synthesized by treating a benzopentalenequinone (BPO) derivative with alkynes that bear an electron-rich aniline moiety
via
a regioselective [4 + 2] cycloaddition (CA) followed by a [4 + 1] retrocycloaddition (RCA). The resulting FOs were readily converted into dibenzodicyanofulvenes (DBDCFs) by treatment with malononitrile in the presence of TiCl
4
and pyridine. The FOs and DBDCFs exhibit intramolecular charge-transfer (ICT) that manifests in absorptions at 350-650 nm and amphoteric electrochemical behavior. Furthermore, FOs and DBDCFs that contain a C&z.tbd;C bond react with tetracyanoethylene in a formal [2 + 2] CA followed by a retro-electrocyclization to afford sterically congested tetracyanobutadiene (TCBD) conjugates. The substituent (H or Me) on the aromatic ring adjacent to the butadiene moiety thereby determines whether the butadiene adopts an s-
cis
or s-
trans
conformation, and thus controls the physicochemical properties of the resulting TCBDs. The TCBD conjugates exhibit ICT absorptions (≤800 nm) together with up to four reversible reduction steps.
We report push-pull fluorenones (FOs) that can be transformed into dibenzodicyanofulvenes (DBDCFs). These FOs and DBDCFs, which contain a C&z.tbd;C bond, can subsequently be converted into tetracyanobutadiene conjugates.</description><subject>Alkynes</subject><subject>Aniline</subject><subject>Aromatic compounds</subject><subject>Butadiene</subject><subject>Charge transfer</subject><subject>Conformation</subject><subject>Conjugates</subject><subject>Crystallography</subject><subject>Cycloaddition</subject><subject>Electrochemical analysis</subject><subject>Electrochemistry</subject><subject>Malononitrile</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Physicochemical properties</subject><subject>Pyridines</subject><subject>Retirement</subject><issn>1477-0520</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp9kUtP3DAUha0KVB7thn1RUDcIKdSP2LHZtSNakEaaDfvI8aOTUWIHOwbRv8MfxTB0QAixulfnfPfaVweAAwRPESTihxK-hbiGbPkJ7KKqrktIidja9BjugL0YVxAiUbPqM9ghGAmEKdoF97OlGTol-2IK0kXrwyCnzrtYeFuMKS7LMfV9Yfvkg3HemXj2StZda9w_rzt1J523qb8xmShkLG5NtnN9GSwL6fT7E-Vk8utPSpsmqbusFcq7VforJxO_gG0r-2i-Ptd9cPX7_Gp2Uc4Xfy5nP-elqrCYSlS3iFOJueTMEkYlk63RLSZc1a1WlWXUVFoJRrmCXFiNoJJQKcoYsYyTfXC8XjsGf51MnJqhiyrfIZ3xKTaY1AJixDnN6Pc36Mqn4PLnGlwhBKmooMjUyZpSwccYjG3G0A0y3DUINo_JNTOx-PWU3EWGD59XpnYweoP-jyoD39ZAiGrjvkSf_aOP_GbUljwA33eufA</recordid><startdate>20200610</startdate><enddate>20200610</enddate><creator>Kato, Shin-ichiro</creator><creator>Kijima, Tomokazu</creator><creator>Shiota, Yoshihito</creator><creator>Abe, Tsukasa</creator><creator>Kuwako, Satoshi</creator><creator>Miyauchi, Hidenori</creator><creator>Yoshikawa, Naoki</creator><creator>Yamamoto, Koji</creator><creator>Yoshizawa, Kazunari</creator><creator>Yoshihara, Toshitada</creator><creator>Tobita, Seiji</creator><creator>Nakamura, Yosuke</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/0000-0003-0866-3207</orcidid><orcidid>https://orcid.org/0000-0002-7960-0740</orcidid><orcidid>https://orcid.org/0000-0002-6047-1336</orcidid><orcidid>https://orcid.org/0000-0003-2054-9845</orcidid><orcidid>https://orcid.org/0000-0002-6279-9722</orcidid><orcidid>https://orcid.org/0000-0001-8024-7318</orcidid><orcidid>https://orcid.org/0000-0001-5310-0062</orcidid></search><sort><creationdate>20200610</creationdate><title>Chemical transformations of push-pull fluorenones: push-pull dibenzodicyanofulvenes as well as fluorenone- and dibenzodicyanofulvene-tetracyanobutadiene conjugates</title><author>Kato, Shin-ichiro ; Kijima, Tomokazu ; Shiota, Yoshihito ; Abe, Tsukasa ; Kuwako, Satoshi ; Miyauchi, Hidenori ; Yoshikawa, Naoki ; Yamamoto, Koji ; Yoshizawa, Kazunari ; Yoshihara, Toshitada ; Tobita, Seiji ; Nakamura, Yosuke</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c429t-17b185a28a86f365a6abedb238c7bdc4f65e4dc9658c089fd10ca0cc5663f683</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Alkynes</topic><topic>Aniline</topic><topic>Aromatic compounds</topic><topic>Butadiene</topic><topic>Charge transfer</topic><topic>Conformation</topic><topic>Conjugates</topic><topic>Crystallography</topic><topic>Cycloaddition</topic><topic>Electrochemical analysis</topic><topic>Electrochemistry</topic><topic>Malononitrile</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Physicochemical properties</topic><topic>Pyridines</topic><topic>Retirement</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kato, Shin-ichiro</creatorcontrib><creatorcontrib>Kijima, Tomokazu</creatorcontrib><creatorcontrib>Shiota, Yoshihito</creatorcontrib><creatorcontrib>Abe, Tsukasa</creatorcontrib><creatorcontrib>Kuwako, Satoshi</creatorcontrib><creatorcontrib>Miyauchi, Hidenori</creatorcontrib><creatorcontrib>Yoshikawa, Naoki</creatorcontrib><creatorcontrib>Yamamoto, Koji</creatorcontrib><creatorcontrib>Yoshizawa, Kazunari</creatorcontrib><creatorcontrib>Yoshihara, Toshitada</creatorcontrib><creatorcontrib>Tobita, Seiji</creatorcontrib><creatorcontrib>Nakamura, Yosuke</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>Kato, Shin-ichiro</au><au>Kijima, Tomokazu</au><au>Shiota, Yoshihito</au><au>Abe, Tsukasa</au><au>Kuwako, Satoshi</au><au>Miyauchi, Hidenori</au><au>Yoshikawa, Naoki</au><au>Yamamoto, Koji</au><au>Yoshizawa, Kazunari</au><au>Yoshihara, Toshitada</au><au>Tobita, Seiji</au><au>Nakamura, Yosuke</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Chemical transformations of push-pull fluorenones: push-pull dibenzodicyanofulvenes as well as fluorenone- and dibenzodicyanofulvene-tetracyanobutadiene conjugates</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2020-06-10</date><risdate>2020</risdate><volume>18</volume><issue>22</issue><spage>4198</spage><epage>429</epage><pages>4198-429</pages><issn>1477-0520</issn><eissn>1477-0539</eissn><abstract>Push-pull fluorenones (FOs) were synthesized by treating a benzopentalenequinone (BPO) derivative with alkynes that bear an electron-rich aniline moiety
via
a regioselective [4 + 2] cycloaddition (CA) followed by a [4 + 1] retrocycloaddition (RCA). The resulting FOs were readily converted into dibenzodicyanofulvenes (DBDCFs) by treatment with malononitrile in the presence of TiCl
4
and pyridine. The FOs and DBDCFs exhibit intramolecular charge-transfer (ICT) that manifests in absorptions at 350-650 nm and amphoteric electrochemical behavior. Furthermore, FOs and DBDCFs that contain a C&z.tbd;C bond react with tetracyanoethylene in a formal [2 + 2] CA followed by a retro-electrocyclization to afford sterically congested tetracyanobutadiene (TCBD) conjugates. The substituent (H or Me) on the aromatic ring adjacent to the butadiene moiety thereby determines whether the butadiene adopts an s-
cis
or s-
trans
conformation, and thus controls the physicochemical properties of the resulting TCBDs. The TCBD conjugates exhibit ICT absorptions (≤800 nm) together with up to four reversible reduction steps.
We report push-pull fluorenones (FOs) that can be transformed into dibenzodicyanofulvenes (DBDCFs). These FOs and DBDCFs, which contain a C&z.tbd;C bond, can subsequently be converted into tetracyanobutadiene conjugates.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>32191251</pmid><doi>10.1039/c9ob02706h</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0003-0866-3207</orcidid><orcidid>https://orcid.org/0000-0002-7960-0740</orcidid><orcidid>https://orcid.org/0000-0002-6047-1336</orcidid><orcidid>https://orcid.org/0000-0003-2054-9845</orcidid><orcidid>https://orcid.org/0000-0002-6279-9722</orcidid><orcidid>https://orcid.org/0000-0001-8024-7318</orcidid><orcidid>https://orcid.org/0000-0001-5310-0062</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-0520 |
| ispartof | Organic & biomolecular chemistry, 2020-06, Vol.18 (22), p.4198-429 |
| issn | 1477-0520 1477-0539 |
| language | eng |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Alkynes Aniline Aromatic compounds Butadiene Charge transfer Conformation Conjugates Crystallography Cycloaddition Electrochemical analysis Electrochemistry Malononitrile NMR Nuclear magnetic resonance Physicochemical properties Pyridines Retirement |
| title | Chemical transformations of push-pull fluorenones: push-pull dibenzodicyanofulvenes as well as fluorenone- and dibenzodicyanofulvene-tetracyanobutadiene conjugates |
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