Application of Rh-Catalyzed Cyclization to the Formation of a Chiral Quaternary Carbon
Rh-Catalyzed cyclization was applied to the formation of a chiral quaternary carbon. It has become clear that the Rh-complex can discriminate between isopropenyl and 2-isopentenyl (or isopentyl) substituents, and the cyclization afforded 3, 3, 4-trisubstituted cyclopentanones with a chiral quaternar...
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| Veröffentlicht in: | Chemical & pharmaceutical bulletin 2000/11/01, Vol.48(11), pp.1822-1825 |
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| container_issue | 11 |
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| container_title | Chemical & pharmaceutical bulletin |
| container_volume | 48 |
| creator | TAKAHASHI, Miyuki TANAKA, Masakazu SAKAMOTO, Eishi IMAI, Masanori FUNAKOSHI, Kazuhisa SAKAI, Kiyoshi SUEMUNE, Hiroshi |
| description | Rh-Catalyzed cyclization was applied to the formation of a chiral quaternary carbon. It has become clear that the Rh-complex can discriminate between isopropenyl and 2-isopentenyl (or isopentyl) substituents, and the cyclization afforded 3, 3, 4-trisubstituted cyclopentanones with a chiral quaternary carbon in a stereoselective manner. The cyclization of 4-pentenals 6a, b by an achiral neutral Rh(PPh3)3Cl afforded 3, 3, 4-cis-trisubstituted cyclopentanones (±)-7a, b in 86-96%, and the cyclization by a cationic Rh[(R)-BINAP]ClO4 afforded 3, 3, 4-trans-trisubstituted cyclopentanones (-)-8a, b of 82-86% ee in 88-98% yields. The mechanism of stereoselection by Rh-complexes is also discussed. |
| doi_str_mv | 10.1248/cpb.48.1822 |
| format | Article |
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It has become clear that the Rh-complex can discriminate between isopropenyl and 2-isopentenyl (or isopentyl) substituents, and the cyclization afforded 3, 3, 4-trisubstituted cyclopentanones with a chiral quaternary carbon in a stereoselective manner. The cyclization of 4-pentenals 6a, b by an achiral neutral Rh(PPh3)3Cl afforded 3, 3, 4-cis-trisubstituted cyclopentanones (±)-7a, b in 86-96%, and the cyclization by a cationic Rh[(R)-BINAP]ClO4 afforded 3, 3, 4-trans-trisubstituted cyclopentanones (-)-8a, b of 82-86% ee in 88-98% yields. The mechanism of stereoselection by Rh-complexes is also discussed.</description><identifier>ISSN: 0009-2363</identifier><identifier>EISSN: 1347-5223</identifier><identifier>DOI: 10.1248/cpb.48.1822</identifier><identifier>PMID: 11086927</identifier><identifier>CODEN: CPBTAL</identifier><language>eng</language><publisher>Tokyo: The Pharmaceutical Society of Japan</publisher><subject>Alicyclic compounds ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; Catalysis ; Chemistry ; Cyclization ; Cyclopentanes - chemical synthesis ; Cyclopentanes - chemistry ; cyclopentanone ; diastereoselective ; enantioselective ; Exact sciences and technology ; Organic chemistry ; Preparations and properties ; quaternary carbon ; Rhodium - chemistry ; Rhodium-catalyzed cyclization ; Stereoisomerism</subject><ispartof>Chemical and Pharmaceutical Bulletin, 2000/11/01, Vol.48(11), pp.1822-1825</ispartof><rights>The Pharmaceutical Society of Japan</rights><rights>2001 INIST-CNRS</rights><rights>Copyright Japan Science and Technology Agency 2000</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c633t-3e51b4a6123317dc1e67493d3323de5583a12e11ef455200d095fefe669e4a0c3</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,1877,27901,27902</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=829689$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11086927$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>TAKAHASHI, Miyuki</creatorcontrib><creatorcontrib>TANAKA, Masakazu</creatorcontrib><creatorcontrib>SAKAMOTO, Eishi</creatorcontrib><creatorcontrib>IMAI, Masanori</creatorcontrib><creatorcontrib>FUNAKOSHI, Kazuhisa</creatorcontrib><creatorcontrib>SAKAI, Kiyoshi</creatorcontrib><creatorcontrib>SUEMUNE, Hiroshi</creatorcontrib><title>Application of Rh-Catalyzed Cyclization to the Formation of a Chiral Quaternary Carbon</title><title>Chemical & pharmaceutical bulletin</title><addtitle>Chem. Pharm. Bull.</addtitle><description>Rh-Catalyzed cyclization was applied to the formation of a chiral quaternary carbon. It has become clear that the Rh-complex can discriminate between isopropenyl and 2-isopentenyl (or isopentyl) substituents, and the cyclization afforded 3, 3, 4-trisubstituted cyclopentanones with a chiral quaternary carbon in a stereoselective manner. The cyclization of 4-pentenals 6a, b by an achiral neutral Rh(PPh3)3Cl afforded 3, 3, 4-cis-trisubstituted cyclopentanones (±)-7a, b in 86-96%, and the cyclization by a cationic Rh[(R)-BINAP]ClO4 afforded 3, 3, 4-trans-trisubstituted cyclopentanones (-)-8a, b of 82-86% ee in 88-98% yields. The mechanism of stereoselection by Rh-complexes is also discussed.</description><subject>Alicyclic compounds</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Cyclization</subject><subject>Cyclopentanes - chemical synthesis</subject><subject>Cyclopentanes - chemistry</subject><subject>cyclopentanone</subject><subject>diastereoselective</subject><subject>enantioselective</subject><subject>Exact sciences and technology</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>quaternary carbon</subject><subject>Rhodium - chemistry</subject><subject>Rhodium-catalyzed cyclization</subject><subject>Stereoisomerism</subject><issn>0009-2363</issn><issn>1347-5223</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2000</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpd0M-L1DAUB_Agiju7evIuBcGLdMzvpsel7LjCgijqNbxJX50OmbYm6WH2rzd1hlnxknfIh_dNvoS8YXTNuDQf3bRdS7NmhvNnZMWErErFuXhOVpTSuuRCiytyHeOeUq5oJV6SK8ao0TWvVuTn7TT53kHqx6EYu-LbrmwggT8-Yls0R-f7x9NdGou0w2IzhsMFQ9Hs-gC--DpDwjBAOBYNhO04vCIvOvARX5_nDfmxufve3JcPXz59bm4fSqeFSKVAxbYSNONCsKp1DHUla9EKwUWLShkBjCNj2EmlOKUtrVWHHWpdowTqxA15f9o7hfH3jDHZQx8deg8DjnO0FZe5IikzfPcf3I9zfrGPlklNc6Axi_pwUi6MMQbs7BT6Q_6WZdQuZdtcts1jKTvrt-ed8_aA7ZM9t_tPKEQHvgswuD5enOG1NnVWm5PaxwS_8HINIfXO4xLJamX-xrLzueQ_gR0Ei4P4A_AknV0</recordid><startdate>20001101</startdate><enddate>20001101</enddate><creator>TAKAHASHI, Miyuki</creator><creator>TANAKA, Masakazu</creator><creator>SAKAMOTO, Eishi</creator><creator>IMAI, Masanori</creator><creator>FUNAKOSHI, Kazuhisa</creator><creator>SAKAI, Kiyoshi</creator><creator>SUEMUNE, Hiroshi</creator><general>The Pharmaceutical Society of Japan</general><general>Maruzen</general><general>Japan Science and Technology Agency</general><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TK</scope><scope>7TM</scope><scope>7U9</scope><scope>H94</scope><scope>7X8</scope></search><sort><creationdate>20001101</creationdate><title>Application of Rh-Catalyzed Cyclization to the Formation of a Chiral Quaternary Carbon</title><author>TAKAHASHI, Miyuki ; TANAKA, Masakazu ; SAKAMOTO, Eishi ; IMAI, Masanori ; FUNAKOSHI, Kazuhisa ; SAKAI, Kiyoshi ; SUEMUNE, Hiroshi</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c633t-3e51b4a6123317dc1e67493d3323de5583a12e11ef455200d095fefe669e4a0c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2000</creationdate><topic>Alicyclic compounds</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Cyclization</topic><topic>Cyclopentanes - chemical synthesis</topic><topic>Cyclopentanes - chemistry</topic><topic>cyclopentanone</topic><topic>diastereoselective</topic><topic>enantioselective</topic><topic>Exact sciences and technology</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>quaternary carbon</topic><topic>Rhodium - chemistry</topic><topic>Rhodium-catalyzed cyclization</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>TAKAHASHI, Miyuki</creatorcontrib><creatorcontrib>TANAKA, Masakazu</creatorcontrib><creatorcontrib>SAKAMOTO, Eishi</creatorcontrib><creatorcontrib>IMAI, Masanori</creatorcontrib><creatorcontrib>FUNAKOSHI, Kazuhisa</creatorcontrib><creatorcontrib>SAKAI, Kiyoshi</creatorcontrib><creatorcontrib>SUEMUNE, Hiroshi</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Neurosciences Abstracts</collection><collection>Nucleic Acids Abstracts</collection><collection>Virology and AIDS Abstracts</collection><collection>AIDS and Cancer Research Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Chemical & pharmaceutical bulletin</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>TAKAHASHI, Miyuki</au><au>TANAKA, Masakazu</au><au>SAKAMOTO, Eishi</au><au>IMAI, Masanori</au><au>FUNAKOSHI, Kazuhisa</au><au>SAKAI, Kiyoshi</au><au>SUEMUNE, Hiroshi</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Application of Rh-Catalyzed Cyclization to the Formation of a Chiral Quaternary Carbon</atitle><jtitle>Chemical & pharmaceutical bulletin</jtitle><addtitle>Chem. Pharm. Bull.</addtitle><date>2000-11-01</date><risdate>2000</risdate><volume>48</volume><issue>11</issue><spage>1822</spage><epage>1825</epage><pages>1822-1825</pages><issn>0009-2363</issn><eissn>1347-5223</eissn><coden>CPBTAL</coden><abstract>Rh-Catalyzed cyclization was applied to the formation of a chiral quaternary carbon. It has become clear that the Rh-complex can discriminate between isopropenyl and 2-isopentenyl (or isopentyl) substituents, and the cyclization afforded 3, 3, 4-trisubstituted cyclopentanones with a chiral quaternary carbon in a stereoselective manner. The cyclization of 4-pentenals 6a, b by an achiral neutral Rh(PPh3)3Cl afforded 3, 3, 4-cis-trisubstituted cyclopentanones (±)-7a, b in 86-96%, and the cyclization by a cationic Rh[(R)-BINAP]ClO4 afforded 3, 3, 4-trans-trisubstituted cyclopentanones (-)-8a, b of 82-86% ee in 88-98% yields. The mechanism of stereoselection by Rh-complexes is also discussed.</abstract><cop>Tokyo</cop><pub>The Pharmaceutical Society of Japan</pub><pmid>11086927</pmid><doi>10.1248/cpb.48.1822</doi><tpages>4</tpages><oa>free_for_read</oa></addata></record> |
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| source | J-STAGE Free; MEDLINE; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; Free Full-Text Journals in Chemistry |
| subjects | Alicyclic compounds Alicyclic compounds, terpenoids, prostaglandins, steroids Catalysis Chemistry Cyclization Cyclopentanes - chemical synthesis Cyclopentanes - chemistry cyclopentanone diastereoselective enantioselective Exact sciences and technology Organic chemistry Preparations and properties quaternary carbon Rhodium - chemistry Rhodium-catalyzed cyclization Stereoisomerism |
| title | Application of Rh-Catalyzed Cyclization to the Formation of a Chiral Quaternary Carbon |
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