Two complementary syntheses of symmetrically-tetrasubstituted cyclooctatetraenes
Two complementary synthetic approaches to tetrasubstituted cyclooctatetraenes (COT's) have been developed. The first approach involves reaction of terminal acetylenes with AlBr[sub 3] and Et[sub 3]N to generate mixtures of 1,3,5,7- and 1,2,5,6-substituted syn-tricyclo[4.2.0.0[sup 2,5]] octadien...
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| Veröffentlicht in: | Journal of organic chemistry 1993-04, Vol.58 (9), p.2377-2380 |
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| container_title | Journal of organic chemistry |
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| creator | Boussie, Thomas R Streitwieser, Andrew |
| description | Two complementary synthetic approaches to tetrasubstituted cyclooctatetraenes (COT's) have been developed. The first approach involves reaction of terminal acetylenes with AlBr[sub 3] and Et[sub 3]N to generate mixtures of 1,3,5,7- and 1,2,5,6-substituted syn-tricyclo[4.2.0.0[sup 2,5]] octadienes (TCOD's) in satisfactory yield. These TCOD's can then be thermally or photolytically ring opened to 1,3,5,7- and 1,2,5,6-substituted COT's. Bulky substituents (e.g., tert-butyl, isopropyl) give exclusively 1,3,5,7-substituted TCOD and COT products. In the second approach, 1,3,5,7- (5) and 1,2,5,6-tetrakis-(hydroxymethyl)COT's (6) were generated and isolated in good yield from the Ni(O)-catalyzed tetramerization of propargyl alcohol. These isomers were converted to their corresponding tetrakis-(bromomethyl)COT's 8 and 9. Reduction of 8 and 9 with LiAlH[sub 4] afforded 1,3,5,7-tetramethylCOT (10) and 1,2,5,6-tetramethylCOT (11). 13 refs. |
| doi_str_mv | 10.1021/jo00061a007 |
| format | Article |
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The first approach involves reaction of terminal acetylenes with AlBr[sub 3] and Et[sub 3]N to generate mixtures of 1,3,5,7- and 1,2,5,6-substituted syn-tricyclo[4.2.0.0[sup 2,5]] octadienes (TCOD's) in satisfactory yield. These TCOD's can then be thermally or photolytically ring opened to 1,3,5,7- and 1,2,5,6-substituted COT's. Bulky substituents (e.g., tert-butyl, isopropyl) give exclusively 1,3,5,7-substituted TCOD and COT products. In the second approach, 1,3,5,7- (5) and 1,2,5,6-tetrakis-(hydroxymethyl)COT's (6) were generated and isolated in good yield from the Ni(O)-catalyzed tetramerization of propargyl alcohol. These isomers were converted to their corresponding tetrakis-(bromomethyl)COT's 8 and 9. Reduction of 8 and 9 with LiAlH[sub 4] afforded 1,3,5,7-tetramethylCOT (10) and 1,2,5,6-tetramethylCOT (11). 13 refs.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo00061a007</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400201 - Chemical & Physicochemical Properties ; Alicyclic compounds ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; ALKANES ; CATALYSIS ; CATALYSTS ; CHEMICAL PREPARATION ; CHEMICAL REACTION YIELD ; CHEMICAL REACTIONS ; Chemistry ; COMPLEXES ; CYCLOALKANES ; Exact sciences and technology ; HOMOGENEOUS CATALYSIS ; HYDROCARBONS ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ISOMERS ; NICKEL COMPLEXES ; Organic chemistry ; ORGANIC COMPOUNDS ; Preparations and properties ; REDUCTION ; SYNTHESIS ; TRANSITION ELEMENT COMPLEXES ; YIELDS</subject><ispartof>Journal of organic chemistry, 1993-04, Vol.58 (9), p.2377-2380</ispartof><rights>1993 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a3097-7d2552b195344b0698f4faf393374a987c859ab03be732a4bf54db671d6c7aaf3</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo00061a007$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo00061a007$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2752,27055,27903,27904,56716,56766</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=4686819$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/5847780$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Boussie, Thomas R</creatorcontrib><creatorcontrib>Streitwieser, Andrew</creatorcontrib><title>Two complementary syntheses of symmetrically-tetrasubstituted cyclooctatetraenes</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Two complementary synthetic approaches to tetrasubstituted cyclooctatetraenes (COT's) have been developed. The first approach involves reaction of terminal acetylenes with AlBr[sub 3] and Et[sub 3]N to generate mixtures of 1,3,5,7- and 1,2,5,6-substituted syn-tricyclo[4.2.0.0[sup 2,5]] octadienes (TCOD's) in satisfactory yield. These TCOD's can then be thermally or photolytically ring opened to 1,3,5,7- and 1,2,5,6-substituted COT's. Bulky substituents (e.g., tert-butyl, isopropyl) give exclusively 1,3,5,7-substituted TCOD and COT products. In the second approach, 1,3,5,7- (5) and 1,2,5,6-tetrakis-(hydroxymethyl)COT's (6) were generated and isolated in good yield from the Ni(O)-catalyzed tetramerization of propargyl alcohol. These isomers were converted to their corresponding tetrakis-(bromomethyl)COT's 8 and 9. Reduction of 8 and 9 with LiAlH[sub 4] afforded 1,3,5,7-tetramethylCOT (10) and 1,2,5,6-tetramethylCOT (11). 13 refs.</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>Alicyclic compounds</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>ALKANES</subject><subject>CATALYSIS</subject><subject>CATALYSTS</subject><subject>CHEMICAL PREPARATION</subject><subject>CHEMICAL REACTION YIELD</subject><subject>CHEMICAL REACTIONS</subject><subject>Chemistry</subject><subject>COMPLEXES</subject><subject>CYCLOALKANES</subject><subject>Exact sciences and technology</subject><subject>HOMOGENEOUS CATALYSIS</subject><subject>HYDROCARBONS</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>ISOMERS</subject><subject>NICKEL COMPLEXES</subject><subject>Organic chemistry</subject><subject>ORGANIC COMPOUNDS</subject><subject>Preparations and properties</subject><subject>REDUCTION</subject><subject>SYNTHESIS</subject><subject>TRANSITION ELEMENT COMPLEXES</subject><subject>YIELDS</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1993</creationdate><recordtype>article</recordtype><recordid>eNpt0F1LwzAUBuAgCs7plX9giOCFVE-ar_ZS5ucYc2D1NqRpyjrbZjQZ2n9vtDK88CoJ50lyzovQKYYrDDG-XlsA4FgBiD00wiyGiKdA99EIII4jEnNyiI6cWwcGjLERWmYfdqJts6lNY1qvun7i-tavjDNuYstwaBrju0qruu4jH7bKbXPnK7_1ppjoXtfWaq9-KqY17hgdlKp25uR3HaPX-7ts-hjNnx-epjfzSBFIRSSKmLE4xykjlObA06SkpSpJSoigKk2ETliqciC5ESRWNC8ZLXIucMG1UAGO0dnwrg3NSKcrb_RK27Y12kuWUCESCOhyQLqzznWmlJuuasKQEoP8Tkz-SSzo80FvlAvzlp1qdeV2VyhPeILTwKKBVc6bz11Zde-SCyKYzJYvcjG7FdlytpBvwV8MXmkX_tt2bcjl3wa-AN0hiBs</recordid><startdate>19930401</startdate><enddate>19930401</enddate><creator>Boussie, Thomas R</creator><creator>Streitwieser, Andrew</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19930401</creationdate><title>Two complementary syntheses of symmetrically-tetrasubstituted cyclooctatetraenes</title><author>Boussie, Thomas R ; Streitwieser, Andrew</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a3097-7d2552b195344b0698f4faf393374a987c859ab03be732a4bf54db671d6c7aaf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1993</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>Alicyclic compounds</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>ALKANES</topic><topic>CATALYSIS</topic><topic>CATALYSTS</topic><topic>CHEMICAL PREPARATION</topic><topic>CHEMICAL REACTION YIELD</topic><topic>CHEMICAL REACTIONS</topic><topic>Chemistry</topic><topic>COMPLEXES</topic><topic>CYCLOALKANES</topic><topic>Exact sciences and technology</topic><topic>HOMOGENEOUS CATALYSIS</topic><topic>HYDROCARBONS</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>ISOMERS</topic><topic>NICKEL COMPLEXES</topic><topic>Organic chemistry</topic><topic>ORGANIC COMPOUNDS</topic><topic>Preparations and properties</topic><topic>REDUCTION</topic><topic>SYNTHESIS</topic><topic>TRANSITION ELEMENT COMPLEXES</topic><topic>YIELDS</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Boussie, Thomas R</creatorcontrib><creatorcontrib>Streitwieser, Andrew</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Boussie, Thomas R</au><au>Streitwieser, Andrew</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Two complementary syntheses of symmetrically-tetrasubstituted cyclooctatetraenes</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>1993-04-01</date><risdate>1993</risdate><volume>58</volume><issue>9</issue><spage>2377</spage><epage>2380</epage><pages>2377-2380</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Two complementary synthetic approaches to tetrasubstituted cyclooctatetraenes (COT's) have been developed. The first approach involves reaction of terminal acetylenes with AlBr[sub 3] and Et[sub 3]N to generate mixtures of 1,3,5,7- and 1,2,5,6-substituted syn-tricyclo[4.2.0.0[sup 2,5]] octadienes (TCOD's) in satisfactory yield. These TCOD's can then be thermally or photolytically ring opened to 1,3,5,7- and 1,2,5,6-substituted COT's. Bulky substituents (e.g., tert-butyl, isopropyl) give exclusively 1,3,5,7-substituted TCOD and COT products. In the second approach, 1,3,5,7- (5) and 1,2,5,6-tetrakis-(hydroxymethyl)COT's (6) were generated and isolated in good yield from the Ni(O)-catalyzed tetramerization of propargyl alcohol. These isomers were converted to their corresponding tetrakis-(bromomethyl)COT's 8 and 9. Reduction of 8 and 9 with LiAlH[sub 4] afforded 1,3,5,7-tetramethylCOT (10) and 1,2,5,6-tetramethylCOT (11). 13 refs.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/jo00061a007</doi><tpages>4</tpages><oa>free_for_read</oa></addata></record> |
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| subjects | 400201 - Chemical & Physicochemical Properties Alicyclic compounds Alicyclic compounds, terpenoids, prostaglandins, steroids ALKANES CATALYSIS CATALYSTS CHEMICAL PREPARATION CHEMICAL REACTION YIELD CHEMICAL REACTIONS Chemistry COMPLEXES CYCLOALKANES Exact sciences and technology HOMOGENEOUS CATALYSIS HYDROCARBONS INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ISOMERS NICKEL COMPLEXES Organic chemistry ORGANIC COMPOUNDS Preparations and properties REDUCTION SYNTHESIS TRANSITION ELEMENT COMPLEXES YIELDS |
| title | Two complementary syntheses of symmetrically-tetrasubstituted cyclooctatetraenes |
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