Isolation and Racemization Mechanism of Optically Active Benzylmethylphenyltelluronium Salts
Diastereomeric benzylmethylphenyltelluronium (1S)‐(+)‐ and (1R)‐(–)‐camphor‐10‐sulfonates were synthesized and resolved by fractional recrystallization. The absolute configurations of the isomers were determined by X‐ray crystallographic analysis. Enantiomerically pure telluronium salts with achiral...
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| Veröffentlicht in: | European Journal of Organic Chemistry 2010-12, Vol.2010 (34), p.6556-6562 |
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| container_title | European Journal of Organic Chemistry |
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| creator | Shimizu, Toshio Sakurai, Ryuuya Azami, Yoko Hirabayashi, Kazunori Kamigata, Nobumasa |
| description | Diastereomeric benzylmethylphenyltelluronium (1S)‐(+)‐ and (1R)‐(–)‐camphor‐10‐sulfonates were synthesized and resolved by fractional recrystallization. The absolute configurations of the isomers were determined by X‐ray crystallographic analysis. Enantiomerically pure telluronium salts with achiral counteranions, such as tetrafluoroborate, 4‐chlorobenzenesulfonate, bromide, iodide, and tetraphenylborate, were also obtained by anion‐exchange reactions of the separated diastereomers. The optically active telluronium salts possessing counteranions with a high nucleophilicity, such as bromide and iodide, were found to racemize in solution. The racemization of the telluronium salts was found to proceed either through the formation of a tellurane by the nucleophilic addition of a counteranion to the tellurium atom followed by decomposition into methyl phenyl telluride and benzyl halide or by several pseudorotations of the tellurane.
Enantiomeric benzylmethylphenyltelluronium salts were isolated with several counteranions. The racemization was found to proceed either through the formation of a tellurane followed by decomposition into achiral methyl phenyl telluride and benzyl halide or by several pseudorotations (Φ) of the tellurane intermediate. |
| doi_str_mv | 10.1002/ejoc.201000893 |
| format | Article |
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Enantiomeric benzylmethylphenyltelluronium salts were isolated with several counteranions. The racemization was found to proceed either through the formation of a tellurane followed by decomposition into achiral methyl phenyl telluride and benzyl halide or by several pseudorotations (Φ) of the tellurane intermediate.</description><identifier>ISSN: 1434-193X</identifier><identifier>EISSN: 1099-0690</identifier><identifier>DOI: 10.1002/ejoc.201000893</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids ; Chemistry ; Chirality ; Circular dichroism ; Configuration determination ; Exact sciences and technology ; Kinetics and mechanisms ; Organic chemistry ; Preparations and properties ; Racemization mechanism ; Reactivity and mechanisms ; Tellurium ; Terpenoids</subject><ispartof>European Journal of Organic Chemistry, 2010-12, Vol.2010 (34), p.6556-6562</ispartof><rights>Copyright © 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2015 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3573-8271e5325c9a6122b579862fea84c9a9443e792b862556c41bda99d77461f0d83</citedby><cites>FETCH-LOGICAL-c3573-8271e5325c9a6122b579862fea84c9a9443e792b862556c41bda99d77461f0d83</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fejoc.201000893$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fejoc.201000893$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>313,314,778,782,790,1414,27909,27911,27912,45561,45562</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=23624404$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Shimizu, Toshio</creatorcontrib><creatorcontrib>Sakurai, Ryuuya</creatorcontrib><creatorcontrib>Azami, Yoko</creatorcontrib><creatorcontrib>Hirabayashi, Kazunori</creatorcontrib><creatorcontrib>Kamigata, Nobumasa</creatorcontrib><title>Isolation and Racemization Mechanism of Optically Active Benzylmethylphenyltelluronium Salts</title><title>European Journal of Organic Chemistry</title><addtitle>Eur. J. Org. Chem</addtitle><description>Diastereomeric benzylmethylphenyltelluronium (1S)‐(+)‐ and (1R)‐(–)‐camphor‐10‐sulfonates were synthesized and resolved by fractional recrystallization. The absolute configurations of the isomers were determined by X‐ray crystallographic analysis. Enantiomerically pure telluronium salts with achiral counteranions, such as tetrafluoroborate, 4‐chlorobenzenesulfonate, bromide, iodide, and tetraphenylborate, were also obtained by anion‐exchange reactions of the separated diastereomers. The optically active telluronium salts possessing counteranions with a high nucleophilicity, such as bromide and iodide, were found to racemize in solution. The racemization of the telluronium salts was found to proceed either through the formation of a tellurane by the nucleophilic addition of a counteranion to the tellurium atom followed by decomposition into methyl phenyl telluride and benzyl halide or by several pseudorotations of the tellurane.
Enantiomeric benzylmethylphenyltelluronium salts were isolated with several counteranions. The racemization was found to proceed either through the formation of a tellurane followed by decomposition into achiral methyl phenyl telluride and benzyl halide or by several pseudorotations (Φ) of the tellurane intermediate.</description><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Chemistry</subject><subject>Chirality</subject><subject>Circular dichroism</subject><subject>Configuration determination</subject><subject>Exact sciences and technology</subject><subject>Kinetics and mechanisms</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Racemization mechanism</subject><subject>Reactivity and mechanisms</subject><subject>Tellurium</subject><subject>Terpenoids</subject><issn>1434-193X</issn><issn>1099-0690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><recordid>eNqFkEtPAjEUhSdGExHdup6Ny8G-pp0ugSBiQKJiNMakKaUTip1HpoM6_HpLxhB3ru7JyfnuzT1BcAlBDwKArvWmUD0EvAYJx0dBBwLOI0A5OPaaYBJBjl9PgzPnNj7DKYWd4H3iCitrU-ShzFfho1Q6M7vWmGm1lrlxWVik4bysjZLWNmFf1eZThwOd7xqb6Xrd2HKt88bW2tptVeRmm4VP0tbuPDhJpXX64nd2g-eb0WJ4G03n48mwP40UjhmOEsSgjjGKFZcUIrSMGU8oSrVMiLc4IVgzjpbei2OqCFyuJOcrxgiFKVgluBv02r2qKpyrdCrKymSyagQEYt-N2HcjDt144KoFSun8U2klc2XcgUKYIkIA8Tne5r6M1c0_W8Xobj78eyNqWeNq_X1gZfUhKMMsFi_3YzGYLd7wA4OC4R9oY4W1</recordid><startdate>201012</startdate><enddate>201012</enddate><creator>Shimizu, Toshio</creator><creator>Sakurai, Ryuuya</creator><creator>Azami, Yoko</creator><creator>Hirabayashi, Kazunori</creator><creator>Kamigata, Nobumasa</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley-VCH</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>201012</creationdate><title>Isolation and Racemization Mechanism of Optically Active Benzylmethylphenyltelluronium Salts</title><author>Shimizu, Toshio ; Sakurai, Ryuuya ; Azami, Yoko ; Hirabayashi, Kazunori ; Kamigata, Nobumasa</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3573-8271e5325c9a6122b579862fea84c9a9443e792b862556c41bda99d77461f0d83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Chemistry</topic><topic>Chirality</topic><topic>Circular dichroism</topic><topic>Configuration determination</topic><topic>Exact sciences and technology</topic><topic>Kinetics and mechanisms</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Racemization mechanism</topic><topic>Reactivity and mechanisms</topic><topic>Tellurium</topic><topic>Terpenoids</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Shimizu, Toshio</creatorcontrib><creatorcontrib>Sakurai, Ryuuya</creatorcontrib><creatorcontrib>Azami, Yoko</creatorcontrib><creatorcontrib>Hirabayashi, Kazunori</creatorcontrib><creatorcontrib>Kamigata, Nobumasa</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><jtitle>European Journal of Organic Chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Shimizu, Toshio</au><au>Sakurai, Ryuuya</au><au>Azami, Yoko</au><au>Hirabayashi, Kazunori</au><au>Kamigata, Nobumasa</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Isolation and Racemization Mechanism of Optically Active Benzylmethylphenyltelluronium Salts</atitle><jtitle>European Journal of Organic Chemistry</jtitle><addtitle>Eur. J. Org. Chem</addtitle><date>2010-12</date><risdate>2010</risdate><volume>2010</volume><issue>34</issue><spage>6556</spage><epage>6562</epage><pages>6556-6562</pages><issn>1434-193X</issn><eissn>1099-0690</eissn><abstract>Diastereomeric benzylmethylphenyltelluronium (1S)‐(+)‐ and (1R)‐(–)‐camphor‐10‐sulfonates were synthesized and resolved by fractional recrystallization. The absolute configurations of the isomers were determined by X‐ray crystallographic analysis. Enantiomerically pure telluronium salts with achiral counteranions, such as tetrafluoroborate, 4‐chlorobenzenesulfonate, bromide, iodide, and tetraphenylborate, were also obtained by anion‐exchange reactions of the separated diastereomers. The optically active telluronium salts possessing counteranions with a high nucleophilicity, such as bromide and iodide, were found to racemize in solution. The racemization of the telluronium salts was found to proceed either through the formation of a tellurane by the nucleophilic addition of a counteranion to the tellurium atom followed by decomposition into methyl phenyl telluride and benzyl halide or by several pseudorotations of the tellurane.
Enantiomeric benzylmethylphenyltelluronium salts were isolated with several counteranions. The racemization was found to proceed either through the formation of a tellurane followed by decomposition into achiral methyl phenyl telluride and benzyl halide or by several pseudorotations (Φ) of the tellurane intermediate.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><doi>10.1002/ejoc.201000893</doi><tpages>7</tpages></addata></record> |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Alicyclic compounds, terpenoids, prostaglandins, steroids Chemistry Chirality Circular dichroism Configuration determination Exact sciences and technology Kinetics and mechanisms Organic chemistry Preparations and properties Racemization mechanism Reactivity and mechanisms Tellurium Terpenoids |
| title | Isolation and Racemization Mechanism of Optically Active Benzylmethylphenyltelluronium Salts |
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