Two‐Step Synthesis of Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post‐synthetic Functionalization
A selective and scalable two‐step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh‐catalyzed stepwise homo Diels...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2020-12, Vol.59 (51), p.23299-23305 |
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| creator | Zieliński, Adam Marset, Xavier Golz, Christopher Wolf, Lawrence M. Alcarazo, Manuel |
| description | A selective and scalable two‐step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh‐catalyzed stepwise homo Diels–Alder cyclisation of NBD into its exo‐cis‐endo dimer. Treatment of this compound with acid promotes its evolution to HCTD via a [1,2]‐sigmatropic rearrangement. The assemblies of 7,12‐disubstituted cages from 7‐(alkyl/aryl) NBDs, as well as the selective post‐synthetic C−H functionalization of the core HCTD scaffold at position C1, or positions C1 and C4 are described.
Heptacyclotetradecane (HCTD) was synthesized through a two‐step process, which starts with the Rh‐catalyzed homo‐Diels Alder between two norbornadiene (nbd) units. Acidic treatment of the thus obtained intermediate affords the desired cage via sigmatropic rearrangement. The post‐synthetic functionalization of the HCTD scaffold is also described. |
| doi_str_mv | 10.1002/anie.202010766 |
| format | Article |
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Heptacyclotetradecane (HCTD) was synthesized through a two‐step process, which starts with the Rh‐catalyzed homo‐Diels Alder between two norbornadiene (nbd) units. Acidic treatment of the thus obtained intermediate affords the desired cage via sigmatropic rearrangement. The post‐synthetic functionalization of the HCTD scaffold is also described.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202010766</identifier><identifier>PMID: 32881255</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Aromatic compounds ; cage compounds ; cationic ligands ; C−H functionalization ; Dimerization ; Dimers ; HCTD ; homo Diels–Alder ; Tetradecane</subject><ispartof>Angewandte Chemie International Edition, 2020-12, Vol.59 (51), p.23299-23305</ispartof><rights>2020 The Authors. Published by Wiley-VCH GmbH</rights><rights>2020 The Authors. Published by Wiley-VCH GmbH.</rights><rights>2020. This article is published under http://creativecommons.org/licenses/by-nc-nd/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5056-9fdddb81aca822e7db51ed3b087fe232e008bdff608b24a46122eb85479db3713</citedby><cites>FETCH-LOGICAL-c5056-9fdddb81aca822e7db51ed3b087fe232e008bdff608b24a46122eb85479db3713</cites><orcidid>0000-0002-5491-5682</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%2Fanie.202010766$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202010766$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,780,784,885,1416,27923,27924,45573,45574</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/32881255$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zieliński, Adam</creatorcontrib><creatorcontrib>Marset, Xavier</creatorcontrib><creatorcontrib>Golz, Christopher</creatorcontrib><creatorcontrib>Wolf, Lawrence M.</creatorcontrib><creatorcontrib>Alcarazo, Manuel</creatorcontrib><title>Two‐Step Synthesis of Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post‐synthetic Functionalization</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>A selective and scalable two‐step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh‐catalyzed stepwise homo Diels–Alder cyclisation of NBD into its exo‐cis‐endo dimer. Treatment of this compound with acid promotes its evolution to HCTD via a [1,2]‐sigmatropic rearrangement. The assemblies of 7,12‐disubstituted cages from 7‐(alkyl/aryl) NBDs, as well as the selective post‐synthetic C−H functionalization of the core HCTD scaffold at position C1, or positions C1 and C4 are described.
Heptacyclotetradecane (HCTD) was synthesized through a two‐step process, which starts with the Rh‐catalyzed homo‐Diels Alder between two norbornadiene (nbd) units. Acidic treatment of the thus obtained intermediate affords the desired cage via sigmatropic rearrangement. The post‐synthetic functionalization of the HCTD scaffold is also described.</description><subject>Aromatic compounds</subject><subject>cage compounds</subject><subject>cationic ligands</subject><subject>C−H functionalization</subject><subject>Dimerization</subject><subject>Dimers</subject><subject>HCTD</subject><subject>homo Diels–Alder</subject><subject>Tetradecane</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkstu1DAUhiMEoqWwZYkssWGRpL7EccICaTRqaaW2ILWsELIc-6TjKrGHOKEaVjwCD8JT8SQ4TBkuG1bnSP78n_9ckuQpwTnBmB4qZyGnmGKCRVneS_YJpyRjQrD7MS8Yy0TFyV7yKISbyFcVLh8meywmhHK-n3y7uvXfv3y9HGGNLjduXEGwAfkWncB6VHqjO_--zMsc55imMbCUsBwXKSE55mmdx7opKT6gEcZBGdDKAWoH36MLPzR-cMpYcPASnYNeRa-hn7VjFbRU14AWIUDfdBuknEFvfRijlfDTxWg1Op6cHq13qrOf1Zw8Th60qgvw5C4eJO-Oj66WJ9nZm9eny8VZpjnmZVa3xpimIkqrilIQpuEEDGtwJVqgjALGVWPatoyBFqooSaSaiheiNg0ThB0kr7a666npwWhwsblOrgfbq2EjvbLy7xdnV_Laf5JC8FKUdRR4cScw-I8ThFH2NmjoujgePwVJC1bXgldYRPT5P-iNn-LcupmKYoXAbHaUbyk9-BAGaHdmCJbzIcj5EOTuEOKHZ3-2sMN_bT4C9Ra4tR1s_iMnFxenR7_FfwBcUcCG</recordid><startdate>20201214</startdate><enddate>20201214</enddate><creator>Zieliński, Adam</creator><creator>Marset, Xavier</creator><creator>Golz, Christopher</creator><creator>Wolf, Lawrence M.</creator><creator>Alcarazo, Manuel</creator><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>24P</scope><scope>WIN</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-5491-5682</orcidid></search><sort><creationdate>20201214</creationdate><title>Two‐Step Synthesis of Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post‐synthetic Functionalization</title><author>Zieliński, Adam ; Marset, Xavier ; Golz, Christopher ; Wolf, Lawrence M. ; Alcarazo, Manuel</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5056-9fdddb81aca822e7db51ed3b087fe232e008bdff608b24a46122eb85479db3713</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Aromatic compounds</topic><topic>cage compounds</topic><topic>cationic ligands</topic><topic>C−H functionalization</topic><topic>Dimerization</topic><topic>Dimers</topic><topic>HCTD</topic><topic>homo Diels–Alder</topic><topic>Tetradecane</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zieliński, Adam</creatorcontrib><creatorcontrib>Marset, Xavier</creatorcontrib><creatorcontrib>Golz, Christopher</creatorcontrib><creatorcontrib>Wolf, Lawrence M.</creatorcontrib><creatorcontrib>Alcarazo, Manuel</creatorcontrib><collection>Wiley-Blackwell Open Access Titles</collection><collection>Wiley Free Content</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zieliński, Adam</au><au>Marset, Xavier</au><au>Golz, Christopher</au><au>Wolf, Lawrence M.</au><au>Alcarazo, Manuel</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Two‐Step Synthesis of Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post‐synthetic Functionalization</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2020-12-14</date><risdate>2020</risdate><volume>59</volume><issue>51</issue><spage>23299</spage><epage>23305</epage><pages>23299-23305</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A selective and scalable two‐step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh‐catalyzed stepwise homo Diels–Alder cyclisation of NBD into its exo‐cis‐endo dimer. Treatment of this compound with acid promotes its evolution to HCTD via a [1,2]‐sigmatropic rearrangement. The assemblies of 7,12‐disubstituted cages from 7‐(alkyl/aryl) NBDs, as well as the selective post‐synthetic C−H functionalization of the core HCTD scaffold at position C1, or positions C1 and C4 are described.
Heptacyclotetradecane (HCTD) was synthesized through a two‐step process, which starts with the Rh‐catalyzed homo‐Diels Alder between two norbornadiene (nbd) units. Acidic treatment of the thus obtained intermediate affords the desired cage via sigmatropic rearrangement. The post‐synthetic functionalization of the HCTD scaffold is also described.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>32881255</pmid><doi>10.1002/anie.202010766</doi><tpages>7</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-5491-5682</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Aromatic compounds cage compounds cationic ligands C−H functionalization Dimerization Dimers HCTD homo Diels–Alder Tetradecane |
| title | Two‐Step Synthesis of Heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post‐synthetic Functionalization |
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