Organocatalytic Enantioselective Higher‐Order Cycloadditions of In Situ Generated Amino Isobenzofulvenes
The [8+2] cycloaddition of indene‐2‐carbaldehydes and nitro olefins is described to provide benzonorbornene scaffolds in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst. This reaction, which proceeds through a transient semi‐aromatic amino iso...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie International Edition 2018-01, Vol.57 (5), p.1246-1250 |
|---|---|
| Hauptverfasser: | , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 1250 |
|---|---|
| container_issue | 5 |
| container_start_page | 1246 |
| container_title | Angewandte Chemie International Edition |
| container_volume | 57 |
| creator | Donslund, Bjarke S. Monleón, Alicia Palazzo, Teresa A. Christensen, Mette Louise Dahlgaard, Anne Erickson, Jeremy D. Jørgensen, Karl Anker |
| description | The [8+2] cycloaddition of indene‐2‐carbaldehydes and nitro olefins is described to provide benzonorbornene scaffolds in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst. This reaction, which proceeds through a transient semi‐aromatic amino isobenzofulvene, represents the first example of catalytic formation and transformation of these species. Quantum chemical calculations suggest a kinetically controlled stepwise mechanism where the stereochemistry is determined in the first bond‐forming event. Beyond the useful [8+2] cycloadducts, [10+4] cycloadducts have been identified in silico as potential off‐pathway intermediates.
After a fashion: Experimental and computational studies detail the catalytic formation and transformation of transient amino isobenzofulvenes by stereoselective [8+2] cycloaddition reactions with electron‐deficient olefins. Benzonorbornene scaffolds are obtained in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst. |
| doi_str_mv | 10.1002/anie.201710694 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1973024165</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1989600094</sourcerecordid><originalsourceid>FETCH-LOGICAL-c4104-6be353a2bab6cfadcda8012293cdde6b99d786933bc12a7c1796866ffccfc9b33</originalsourceid><addsrcrecordid>eNqF0c1OGzEUBWCrAgFNu2WJLHXTzQT_TOzxMopSGAk1C9r1yGPfoY4mdmrPBKWrPgLPyJPUKEAlNqx8JX8-uvJB6JySKSWEXWrvYMoIlZQIVX5AZ3TGaMGl5Ed5LjkvZDWjp-hjSuvsq4qIE3TKFCOCc3mG1qt4p30wetD9fnAGL732gwsJejCD2wG-dne_ID7-fVhFCxEv9qYP2lqXkU84dLj2-NYNI74CD1EPYPF843zAdQot-D-hG_tdvkqf0HGn-wSfn88J-vlt-WNxXdysrurF_KYwJSVlIVrgM65Zq1thOm2N1RWhjClurAXRKmVlJRTnraFMS0OlEpUQXWdMZ1TL-QR9PeRuY_g9QhqajUsG-l57CGNqqJKcsJKKWaZf3tB1GKPP22VVKUEIUWVW04MyMaQUoWu20W103DeUNE8tNE8tNK8t5AcXz7FjuwH7yl--PQN1APeuh_07cc38e738H_4PllOWng</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1989600094</pqid></control><display><type>article</type><title>Organocatalytic Enantioselective Higher‐Order Cycloadditions of In Situ Generated Amino Isobenzofulvenes</title><source>Wiley Online Library All Journals</source><creator>Donslund, Bjarke S. ; Monleón, Alicia ; Palazzo, Teresa A. ; Christensen, Mette Louise ; Dahlgaard, Anne ; Erickson, Jeremy D. ; Jørgensen, Karl Anker</creator><creatorcontrib>Donslund, Bjarke S. ; Monleón, Alicia ; Palazzo, Teresa A. ; Christensen, Mette Louise ; Dahlgaard, Anne ; Erickson, Jeremy D. ; Jørgensen, Karl Anker</creatorcontrib><description>The [8+2] cycloaddition of indene‐2‐carbaldehydes and nitro olefins is described to provide benzonorbornene scaffolds in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst. This reaction, which proceeds through a transient semi‐aromatic amino isobenzofulvene, represents the first example of catalytic formation and transformation of these species. Quantum chemical calculations suggest a kinetically controlled stepwise mechanism where the stereochemistry is determined in the first bond‐forming event. Beyond the useful [8+2] cycloadducts, [10+4] cycloadducts have been identified in silico as potential off‐pathway intermediates.
After a fashion: Experimental and computational studies detail the catalytic formation and transformation of transient amino isobenzofulvenes by stereoselective [8+2] cycloaddition reactions with electron‐deficient olefins. Benzonorbornene scaffolds are obtained in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201710694</identifier><identifier>PMID: 29206337</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Alkenes ; Catalysis ; Cycloaddition ; Enantiomers ; enantioselectivity ; fulvenes ; Indene ; Intermediates ; organocatalysis ; Quantum chemistry ; reaction mechanisms ; Scaffolds ; Stereochemistry</subject><ispartof>Angewandte Chemie International Edition, 2018-01, Vol.57 (5), p.1246-1250</ispartof><rights>2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4104-6be353a2bab6cfadcda8012293cdde6b99d786933bc12a7c1796866ffccfc9b33</citedby><cites>FETCH-LOGICAL-c4104-6be353a2bab6cfadcda8012293cdde6b99d786933bc12a7c1796866ffccfc9b33</cites><orcidid>0000-0002-3482-6236</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.201710694$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201710694$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1416,27923,27924,45573,45574</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29206337$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Donslund, Bjarke S.</creatorcontrib><creatorcontrib>Monleón, Alicia</creatorcontrib><creatorcontrib>Palazzo, Teresa A.</creatorcontrib><creatorcontrib>Christensen, Mette Louise</creatorcontrib><creatorcontrib>Dahlgaard, Anne</creatorcontrib><creatorcontrib>Erickson, Jeremy D.</creatorcontrib><creatorcontrib>Jørgensen, Karl Anker</creatorcontrib><title>Organocatalytic Enantioselective Higher‐Order Cycloadditions of In Situ Generated Amino Isobenzofulvenes</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>The [8+2] cycloaddition of indene‐2‐carbaldehydes and nitro olefins is described to provide benzonorbornene scaffolds in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst. This reaction, which proceeds through a transient semi‐aromatic amino isobenzofulvene, represents the first example of catalytic formation and transformation of these species. Quantum chemical calculations suggest a kinetically controlled stepwise mechanism where the stereochemistry is determined in the first bond‐forming event. Beyond the useful [8+2] cycloadducts, [10+4] cycloadducts have been identified in silico as potential off‐pathway intermediates.
After a fashion: Experimental and computational studies detail the catalytic formation and transformation of transient amino isobenzofulvenes by stereoselective [8+2] cycloaddition reactions with electron‐deficient olefins. Benzonorbornene scaffolds are obtained in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst.</description><subject>Alkenes</subject><subject>Catalysis</subject><subject>Cycloaddition</subject><subject>Enantiomers</subject><subject>enantioselectivity</subject><subject>fulvenes</subject><subject>Indene</subject><subject>Intermediates</subject><subject>organocatalysis</subject><subject>Quantum chemistry</subject><subject>reaction mechanisms</subject><subject>Scaffolds</subject><subject>Stereochemistry</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNqF0c1OGzEUBWCrAgFNu2WJLHXTzQT_TOzxMopSGAk1C9r1yGPfoY4mdmrPBKWrPgLPyJPUKEAlNqx8JX8-uvJB6JySKSWEXWrvYMoIlZQIVX5AZ3TGaMGl5Ed5LjkvZDWjp-hjSuvsq4qIE3TKFCOCc3mG1qt4p30wetD9fnAGL732gwsJejCD2wG-dne_ID7-fVhFCxEv9qYP2lqXkU84dLj2-NYNI74CD1EPYPF843zAdQot-D-hG_tdvkqf0HGn-wSfn88J-vlt-WNxXdysrurF_KYwJSVlIVrgM65Zq1thOm2N1RWhjClurAXRKmVlJRTnraFMS0OlEpUQXWdMZ1TL-QR9PeRuY_g9QhqajUsG-l57CGNqqJKcsJKKWaZf3tB1GKPP22VVKUEIUWVW04MyMaQUoWu20W103DeUNE8tNE8tNK8t5AcXz7FjuwH7yl--PQN1APeuh_07cc38e738H_4PllOWng</recordid><startdate>20180126</startdate><enddate>20180126</enddate><creator>Donslund, Bjarke S.</creator><creator>Monleón, Alicia</creator><creator>Palazzo, Teresa A.</creator><creator>Christensen, Mette Louise</creator><creator>Dahlgaard, Anne</creator><creator>Erickson, Jeremy D.</creator><creator>Jørgensen, Karl Anker</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-3482-6236</orcidid></search><sort><creationdate>20180126</creationdate><title>Organocatalytic Enantioselective Higher‐Order Cycloadditions of In Situ Generated Amino Isobenzofulvenes</title><author>Donslund, Bjarke S. ; Monleón, Alicia ; Palazzo, Teresa A. ; Christensen, Mette Louise ; Dahlgaard, Anne ; Erickson, Jeremy D. ; Jørgensen, Karl Anker</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4104-6be353a2bab6cfadcda8012293cdde6b99d786933bc12a7c1796866ffccfc9b33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Alkenes</topic><topic>Catalysis</topic><topic>Cycloaddition</topic><topic>Enantiomers</topic><topic>enantioselectivity</topic><topic>fulvenes</topic><topic>Indene</topic><topic>Intermediates</topic><topic>organocatalysis</topic><topic>Quantum chemistry</topic><topic>reaction mechanisms</topic><topic>Scaffolds</topic><topic>Stereochemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Donslund, Bjarke S.</creatorcontrib><creatorcontrib>Monleón, Alicia</creatorcontrib><creatorcontrib>Palazzo, Teresa A.</creatorcontrib><creatorcontrib>Christensen, Mette Louise</creatorcontrib><creatorcontrib>Dahlgaard, Anne</creatorcontrib><creatorcontrib>Erickson, Jeremy D.</creatorcontrib><creatorcontrib>Jørgensen, Karl Anker</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Donslund, Bjarke S.</au><au>Monleón, Alicia</au><au>Palazzo, Teresa A.</au><au>Christensen, Mette Louise</au><au>Dahlgaard, Anne</au><au>Erickson, Jeremy D.</au><au>Jørgensen, Karl Anker</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Organocatalytic Enantioselective Higher‐Order Cycloadditions of In Situ Generated Amino Isobenzofulvenes</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2018-01-26</date><risdate>2018</risdate><volume>57</volume><issue>5</issue><spage>1246</spage><epage>1250</epage><pages>1246-1250</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>The [8+2] cycloaddition of indene‐2‐carbaldehydes and nitro olefins is described to provide benzonorbornene scaffolds in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst. This reaction, which proceeds through a transient semi‐aromatic amino isobenzofulvene, represents the first example of catalytic formation and transformation of these species. Quantum chemical calculations suggest a kinetically controlled stepwise mechanism where the stereochemistry is determined in the first bond‐forming event. Beyond the useful [8+2] cycloadducts, [10+4] cycloadducts have been identified in silico as potential off‐pathway intermediates.
After a fashion: Experimental and computational studies detail the catalytic formation and transformation of transient amino isobenzofulvenes by stereoselective [8+2] cycloaddition reactions with electron‐deficient olefins. Benzonorbornene scaffolds are obtained in a highly peri‐, diastereo‐, and enantioselective fashion in the presence of a C2‐symmetric aminocatalyst.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>29206337</pmid><doi>10.1002/anie.201710694</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-3482-6236</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1433-7851 |
| ispartof | Angewandte Chemie International Edition, 2018-01, Vol.57 (5), p.1246-1250 |
| issn | 1433-7851 1521-3773 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_1973024165 |
| source | Wiley Online Library All Journals |
| subjects | Alkenes Catalysis Cycloaddition Enantiomers enantioselectivity fulvenes Indene Intermediates organocatalysis Quantum chemistry reaction mechanisms Scaffolds Stereochemistry |
| title | Organocatalytic Enantioselective Higher‐Order Cycloadditions of In Situ Generated Amino Isobenzofulvenes |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-12T10%3A46%3A02IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Organocatalytic%20Enantioselective%20Higher%E2%80%90Order%20Cycloadditions%20of%20In%20Situ%20Generated%20Amino%20Isobenzofulvenes&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Donslund,%20Bjarke%20S.&rft.date=2018-01-26&rft.volume=57&rft.issue=5&rft.spage=1246&rft.epage=1250&rft.pages=1246-1250&rft.issn=1433-7851&rft.eissn=1521-3773&rft_id=info:doi/10.1002/anie.201710694&rft_dat=%3Cproquest_cross%3E1989600094%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1989600094&rft_id=info:pmid/29206337&rfr_iscdi=true |