Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity
Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh 3 and Rh/ tris-( o- t-butylphenyl)phosphite catalytic systems. For the three substrates, t...
Gespeichert in:
| Veröffentlicht in: | Applied catalysis. A, General General, 2008-06, Vol.340 (2), p.212-219 |
|---|---|
| Hauptverfasser: | , , , , , , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 219 |
|---|---|
| container_issue | 2 |
| container_start_page | 212 |
| container_title | Applied catalysis. A, General |
| container_volume | 340 |
| creator | Peixoto, Andreia F. de Melo, Daniela S. Fernandes, Tânia F. Fonseca, Yuraima Gusevskaya, Elena V. Silva, Artur M.S. Contreras, Ricardo R. Reyes, Marisela Usubillaga, Alfredo dos Santos, Eduardo N. Pereira, Mariette M. Bayón, J. Carles |
| description | Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems. For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes.
▪
Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. Both acids contain an exocyclic methylenic double bond that allows further functionalization on their structure. In an attempt to expand the number of derivatives of these two natural products, we have undertaken a study on the hydroformylation of the methyl esters of the two acids and the trimethylsilyl ether of kaurenol. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems at 100
°C and 20
bar of CO/H
2 (1:1). For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes. In all cases, the stereoselectivity observed is strongly dependent of the system used, being the most diastereoselective the least hindered unmodified Rh/CO catalyst. A correlation between the higher diastereoselectivity and the faster β-elimination of the metal-alkyl intermediate observed in the unmodified system is discussed. |
| doi_str_mv | 10.1016/j.apcata.2008.02.015 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_33455779</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S0926860X08001026</els_id><sourcerecordid>33455779</sourcerecordid><originalsourceid>FETCH-LOGICAL-c413t-e53699657b36633091b000b90d7a59b47ed60432815d49e8cc18f93c749248413</originalsourceid><addsrcrecordid>eNp9kE-LFDEQxYMoOK5-Aw-56K1787fT8SAsy6oLC4IoeAvppJrJ2NNpk_Qs7ac3wywePRUU772q90PoLSUtJbS7PrR2cbbYlhHSt4S1hMpnaEd7xRveK_kc7YhmXdN35OdL9CrnAyGECS13KH7bRx_WIz77p-0PeLzffIpjTMdtsiXEGccR_7JrsjNgDymc6vYE-QO-wSmuBXCJeIZH7EOBtMAMGT-GssdLLDCXYCc8hGhdNYWyvUYvRjtlePM0r9CPT3ffb780D18_39_ePDROUF4akLzTupNq4F3HOdF0qC8PmnhlpR6EAt8RwVlPpRcaeudoP2rulNBM9DXiCr2_5C4p_l4hF3MM2cE01RZxzYZzIaVSugrFRehSzDnBaJYUjjZthhJzpmsO5kLXnOkawkylW23vnvJtdnYaKx0X8j8vI5wppc66jxcd1LKnAMlkF2B24EMCV4yP4f-H_gJWKZMs</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>33455779</pqid></control><display><type>article</type><title>Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity</title><source>Elsevier ScienceDirect Journals</source><creator>Peixoto, Andreia F. ; de Melo, Daniela S. ; Fernandes, Tânia F. ; Fonseca, Yuraima ; Gusevskaya, Elena V. ; Silva, Artur M.S. ; Contreras, Ricardo R. ; Reyes, Marisela ; Usubillaga, Alfredo ; dos Santos, Eduardo N. ; Pereira, Mariette M. ; Bayón, J. Carles</creator><creatorcontrib>Peixoto, Andreia F. ; de Melo, Daniela S. ; Fernandes, Tânia F. ; Fonseca, Yuraima ; Gusevskaya, Elena V. ; Silva, Artur M.S. ; Contreras, Ricardo R. ; Reyes, Marisela ; Usubillaga, Alfredo ; dos Santos, Eduardo N. ; Pereira, Mariette M. ; Bayón, J. Carles</creatorcontrib><description>Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems. For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes.
▪
Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. Both acids contain an exocyclic methylenic double bond that allows further functionalization on their structure. In an attempt to expand the number of derivatives of these two natural products, we have undertaken a study on the hydroformylation of the methyl esters of the two acids and the trimethylsilyl ether of kaurenol. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems at 100
°C and 20
bar of CO/H
2 (1:1). For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes. In all cases, the stereoselectivity observed is strongly dependent of the system used, being the most diastereoselective the least hindered unmodified Rh/CO catalyst. A correlation between the higher diastereoselectivity and the faster β-elimination of the metal-alkyl intermediate observed in the unmodified system is discussed.</description><identifier>ISSN: 0926-860X</identifier><identifier>EISSN: 1873-3875</identifier><identifier>DOI: 10.1016/j.apcata.2008.02.015</identifier><language>eng</language><publisher>Amsterdam: Elsevier B.V</publisher><subject>Catalysis ; Chemistry ; Diterpenes ; Exact sciences and technology ; General and physical chemistry ; Hydroformylation ; Kauranes ; Phosphine ; Phosphite ; Rhodium ; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><ispartof>Applied catalysis. A, General, 2008-06, Vol.340 (2), p.212-219</ispartof><rights>2008 Elsevier B.V.</rights><rights>2008 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c413t-e53699657b36633091b000b90d7a59b47ed60432815d49e8cc18f93c749248413</citedby><cites>FETCH-LOGICAL-c413t-e53699657b36633091b000b90d7a59b47ed60432815d49e8cc18f93c749248413</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.apcata.2008.02.015$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,777,781,3537,27905,27906,45976</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=20327775$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Peixoto, Andreia F.</creatorcontrib><creatorcontrib>de Melo, Daniela S.</creatorcontrib><creatorcontrib>Fernandes, Tânia F.</creatorcontrib><creatorcontrib>Fonseca, Yuraima</creatorcontrib><creatorcontrib>Gusevskaya, Elena V.</creatorcontrib><creatorcontrib>Silva, Artur M.S.</creatorcontrib><creatorcontrib>Contreras, Ricardo R.</creatorcontrib><creatorcontrib>Reyes, Marisela</creatorcontrib><creatorcontrib>Usubillaga, Alfredo</creatorcontrib><creatorcontrib>dos Santos, Eduardo N.</creatorcontrib><creatorcontrib>Pereira, Mariette M.</creatorcontrib><creatorcontrib>Bayón, J. Carles</creatorcontrib><title>Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity</title><title>Applied catalysis. A, General</title><description>Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems. For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes.
▪
Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. Both acids contain an exocyclic methylenic double bond that allows further functionalization on their structure. In an attempt to expand the number of derivatives of these two natural products, we have undertaken a study on the hydroformylation of the methyl esters of the two acids and the trimethylsilyl ether of kaurenol. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems at 100
°C and 20
bar of CO/H
2 (1:1). For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes. In all cases, the stereoselectivity observed is strongly dependent of the system used, being the most diastereoselective the least hindered unmodified Rh/CO catalyst. A correlation between the higher diastereoselectivity and the faster β-elimination of the metal-alkyl intermediate observed in the unmodified system is discussed.</description><subject>Catalysis</subject><subject>Chemistry</subject><subject>Diterpenes</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Hydroformylation</subject><subject>Kauranes</subject><subject>Phosphine</subject><subject>Phosphite</subject><subject>Rhodium</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><issn>0926-860X</issn><issn>1873-3875</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><recordid>eNp9kE-LFDEQxYMoOK5-Aw-56K1787fT8SAsy6oLC4IoeAvppJrJ2NNpk_Qs7ac3wywePRUU772q90PoLSUtJbS7PrR2cbbYlhHSt4S1hMpnaEd7xRveK_kc7YhmXdN35OdL9CrnAyGECS13KH7bRx_WIz77p-0PeLzffIpjTMdtsiXEGccR_7JrsjNgDymc6vYE-QO-wSmuBXCJeIZH7EOBtMAMGT-GssdLLDCXYCc8hGhdNYWyvUYvRjtlePM0r9CPT3ffb780D18_39_ePDROUF4akLzTupNq4F3HOdF0qC8PmnhlpR6EAt8RwVlPpRcaeudoP2rulNBM9DXiCr2_5C4p_l4hF3MM2cE01RZxzYZzIaVSugrFRehSzDnBaJYUjjZthhJzpmsO5kLXnOkawkylW23vnvJtdnYaKx0X8j8vI5wppc66jxcd1LKnAMlkF2B24EMCV4yP4f-H_gJWKZMs</recordid><startdate>20080601</startdate><enddate>20080601</enddate><creator>Peixoto, Andreia F.</creator><creator>de Melo, Daniela S.</creator><creator>Fernandes, Tânia F.</creator><creator>Fonseca, Yuraima</creator><creator>Gusevskaya, Elena V.</creator><creator>Silva, Artur M.S.</creator><creator>Contreras, Ricardo R.</creator><creator>Reyes, Marisela</creator><creator>Usubillaga, Alfredo</creator><creator>dos Santos, Eduardo N.</creator><creator>Pereira, Mariette M.</creator><creator>Bayón, J. Carles</creator><general>Elsevier B.V</general><general>Elsevier</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20080601</creationdate><title>Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity</title><author>Peixoto, Andreia F. ; de Melo, Daniela S. ; Fernandes, Tânia F. ; Fonseca, Yuraima ; Gusevskaya, Elena V. ; Silva, Artur M.S. ; Contreras, Ricardo R. ; Reyes, Marisela ; Usubillaga, Alfredo ; dos Santos, Eduardo N. ; Pereira, Mariette M. ; Bayón, J. Carles</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c413t-e53699657b36633091b000b90d7a59b47ed60432815d49e8cc18f93c749248413</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>Catalysis</topic><topic>Chemistry</topic><topic>Diterpenes</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Hydroformylation</topic><topic>Kauranes</topic><topic>Phosphine</topic><topic>Phosphite</topic><topic>Rhodium</topic><topic>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Peixoto, Andreia F.</creatorcontrib><creatorcontrib>de Melo, Daniela S.</creatorcontrib><creatorcontrib>Fernandes, Tânia F.</creatorcontrib><creatorcontrib>Fonseca, Yuraima</creatorcontrib><creatorcontrib>Gusevskaya, Elena V.</creatorcontrib><creatorcontrib>Silva, Artur M.S.</creatorcontrib><creatorcontrib>Contreras, Ricardo R.</creatorcontrib><creatorcontrib>Reyes, Marisela</creatorcontrib><creatorcontrib>Usubillaga, Alfredo</creatorcontrib><creatorcontrib>dos Santos, Eduardo N.</creatorcontrib><creatorcontrib>Pereira, Mariette M.</creatorcontrib><creatorcontrib>Bayón, J. Carles</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Applied catalysis. A, General</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Peixoto, Andreia F.</au><au>de Melo, Daniela S.</au><au>Fernandes, Tânia F.</au><au>Fonseca, Yuraima</au><au>Gusevskaya, Elena V.</au><au>Silva, Artur M.S.</au><au>Contreras, Ricardo R.</au><au>Reyes, Marisela</au><au>Usubillaga, Alfredo</au><au>dos Santos, Eduardo N.</au><au>Pereira, Mariette M.</au><au>Bayón, J. Carles</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity</atitle><jtitle>Applied catalysis. A, General</jtitle><date>2008-06-01</date><risdate>2008</risdate><volume>340</volume><issue>2</issue><spage>212</spage><epage>219</epage><pages>212-219</pages><issn>0926-860X</issn><eissn>1873-3875</eissn><abstract>Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems. For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes.
▪
Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. Both acids contain an exocyclic methylenic double bond that allows further functionalization on their structure. In an attempt to expand the number of derivatives of these two natural products, we have undertaken a study on the hydroformylation of the methyl esters of the two acids and the trimethylsilyl ether of kaurenol. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh
3 and Rh/
tris-(
o-
t-butylphenyl)phosphite catalytic systems at 100
°C and 20
bar of CO/H
2 (1:1). For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes. In all cases, the stereoselectivity observed is strongly dependent of the system used, being the most diastereoselective the least hindered unmodified Rh/CO catalyst. A correlation between the higher diastereoselectivity and the faster β-elimination of the metal-alkyl intermediate observed in the unmodified system is discussed.</abstract><cop>Amsterdam</cop><pub>Elsevier B.V</pub><doi>10.1016/j.apcata.2008.02.015</doi><tpages>8</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0926-860X |
| ispartof | Applied catalysis. A, General, 2008-06, Vol.340 (2), p.212-219 |
| issn | 0926-860X 1873-3875 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_33455779 |
| source | Elsevier ScienceDirect Journals |
| subjects | Catalysis Chemistry Diterpenes Exact sciences and technology General and physical chemistry Hydroformylation Kauranes Phosphine Phosphite Rhodium Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry |
| title | Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-19T14%3A45%3A50IST&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=Rhodium%20catalyzed%20hydroformylation%20of%20kaurane%20derivatives:%20A%20route%20to%20new%20diterpenes%20with%20potential%20bioactivity&rft.jtitle=Applied%20catalysis.%20A,%20General&rft.au=Peixoto,%20Andreia%20F.&rft.date=2008-06-01&rft.volume=340&rft.issue=2&rft.spage=212&rft.epage=219&rft.pages=212-219&rft.issn=0926-860X&rft.eissn=1873-3875&rft_id=info:doi/10.1016/j.apcata.2008.02.015&rft_dat=%3Cproquest_cross%3E33455779%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=33455779&rft_id=info:pmid/&rft_els_id=S0926860X08001026&rfr_iscdi=true |