Reaction Pathway of Methylenation of Carbonyl Compounds with Bis(iodozincio)methane
About 40 years have passed since methylene dizinc reagent was discovered as a substitute for Wittig reagent. Density functional theory (DFT) calculations have been performed to understand the reaction pathways of methylenation of carbonyl compounds with bis(iodozincio)methane. The present computatio...
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| Veröffentlicht in: | Journal of the American Chemical Society 2010-12, Vol.132 (49), p.17452-17458 |
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| container_end_page | 17458 |
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| container_issue | 49 |
| container_start_page | 17452 |
| container_title | Journal of the American Chemical Society |
| container_volume | 132 |
| creator | Sada, Mutsumi Komagawa, Shinsuke Uchiyama, Masanobu Kobata, Masami Mizuno, Tsuyoshi Utimoto, Kiitiro Oshima, Koichiro Matsubara, Seijiro |
| description | About 40 years have passed since methylene dizinc reagent was discovered as a substitute for Wittig reagent. Density functional theory (DFT) calculations have been performed to understand the reaction pathways of methylenation of carbonyl compounds with bis(iodozincio)methane. The present computational/theoretical study concluded that the methylenation reaction with gem-dizinc reagent proceeds as a two-step reaction, that is, methylene addition (RDS) and olefination. In the first step, the nucleophilic attack of the CH2 group enhanced by two Zn proceeds under the assistance of the electrophilic activation of the carbonyl group with the Zn atom. In the second step, the olefination is facilitated by both Zn atoms of the gem-dizinc reagent without an electron transfer process. |
| doi_str_mv | 10.1021/ja104439w |
| format | Article |
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Density functional theory (DFT) calculations have been performed to understand the reaction pathways of methylenation of carbonyl compounds with bis(iodozincio)methane. The present computational/theoretical study concluded that the methylenation reaction with gem-dizinc reagent proceeds as a two-step reaction, that is, methylene addition (RDS) and olefination. In the first step, the nucleophilic attack of the CH2 group enhanced by two Zn proceeds under the assistance of the electrophilic activation of the carbonyl group with the Zn atom. In the second step, the olefination is facilitated by both Zn atoms of the gem-dizinc reagent without an electron transfer process.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja104439w</identifier><identifier>PMID: 21082850</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Aldehydes - chemistry ; Alkenes - chemistry ; Carboxylic Acids - chemistry ; Indicators and Reagents ; Ketones - chemistry ; Methane - analogs & derivatives ; Methane - chemistry</subject><ispartof>Journal of the American Chemical Society, 2010-12, Vol.132 (49), p.17452-17458</ispartof><rights>Copyright © 2010 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a359t-781625ee8e2934cc6d4ed575d4a94ace7dabaa0750667f8f904d6342dd2d752e3</citedby><cites>FETCH-LOGICAL-a359t-781625ee8e2934cc6d4ed575d4a94ace7dabaa0750667f8f904d6342dd2d752e3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja104439w$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja104439w$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,777,781,2752,27057,27905,27906,56719,56769</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/21082850$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Sada, Mutsumi</creatorcontrib><creatorcontrib>Komagawa, Shinsuke</creatorcontrib><creatorcontrib>Uchiyama, Masanobu</creatorcontrib><creatorcontrib>Kobata, Masami</creatorcontrib><creatorcontrib>Mizuno, Tsuyoshi</creatorcontrib><creatorcontrib>Utimoto, Kiitiro</creatorcontrib><creatorcontrib>Oshima, Koichiro</creatorcontrib><creatorcontrib>Matsubara, Seijiro</creatorcontrib><title>Reaction Pathway of Methylenation of Carbonyl Compounds with Bis(iodozincio)methane</title><title>Journal of the American Chemical Society</title><addtitle>J. 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In the second step, the olefination is facilitated by both Zn atoms of the gem-dizinc reagent without an electron transfer process.</description><subject>Aldehydes - chemistry</subject><subject>Alkenes - chemistry</subject><subject>Carboxylic Acids - chemistry</subject><subject>Indicators and Reagents</subject><subject>Ketones - chemistry</subject><subject>Methane - analogs & derivatives</subject><subject>Methane - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkMtOwzAQRS0EoqWw4AdQNkjtImA7tpMsIeIlgUA81tHUdlRXSVzsRFX4egwtXbEazcyZqzsXoVOCLwim5HIJBDOW5Os9NCac4pgTKvbRGGNM4zQTyQgdeb8MLaMZOUQjSnBGM47H6O1Vg-yMbaMX6BZrGCJbRU-6Wwy1buF3EQYFuLlthzoqbLOyfat8tDbdIro2fmqssl-mlcbOmnAHrT5GBxXUXp9s6wR93N68F_fx4_PdQ3H1GEPC8y4YI4JyrTNN84RJKRTTiqdcMcgZSJ0qmAPglGMh0iqrcsyUSBhViqqUU51M0HSju3L2s9e-Kxvjpa7r4MH2viQJyQXNQwgBnW1Q6az3TlflypkG3FASXP5kWO4yDOzZVrafN1rtyL_QAnC-AUD6cml714Yv_xH6Br45eHM</recordid><startdate>20101215</startdate><enddate>20101215</enddate><creator>Sada, Mutsumi</creator><creator>Komagawa, Shinsuke</creator><creator>Uchiyama, Masanobu</creator><creator>Kobata, Masami</creator><creator>Mizuno, Tsuyoshi</creator><creator>Utimoto, Kiitiro</creator><creator>Oshima, Koichiro</creator><creator>Matsubara, Seijiro</creator><general>American Chemical Society</general><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>7X8</scope></search><sort><creationdate>20101215</creationdate><title>Reaction Pathway of Methylenation of Carbonyl Compounds with Bis(iodozincio)methane</title><author>Sada, Mutsumi ; Komagawa, Shinsuke ; Uchiyama, Masanobu ; Kobata, Masami ; Mizuno, Tsuyoshi ; Utimoto, Kiitiro ; Oshima, Koichiro ; Matsubara, Seijiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a359t-781625ee8e2934cc6d4ed575d4a94ace7dabaa0750667f8f904d6342dd2d752e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Aldehydes - chemistry</topic><topic>Alkenes - chemistry</topic><topic>Carboxylic Acids - chemistry</topic><topic>Indicators and Reagents</topic><topic>Ketones - chemistry</topic><topic>Methane - analogs & derivatives</topic><topic>Methane - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Sada, Mutsumi</creatorcontrib><creatorcontrib>Komagawa, Shinsuke</creatorcontrib><creatorcontrib>Uchiyama, Masanobu</creatorcontrib><creatorcontrib>Kobata, Masami</creatorcontrib><creatorcontrib>Mizuno, Tsuyoshi</creatorcontrib><creatorcontrib>Utimoto, Kiitiro</creatorcontrib><creatorcontrib>Oshima, Koichiro</creatorcontrib><creatorcontrib>Matsubara, Seijiro</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Sada, Mutsumi</au><au>Komagawa, Shinsuke</au><au>Uchiyama, Masanobu</au><au>Kobata, Masami</au><au>Mizuno, Tsuyoshi</au><au>Utimoto, Kiitiro</au><au>Oshima, Koichiro</au><au>Matsubara, Seijiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reaction Pathway of Methylenation of Carbonyl Compounds with Bis(iodozincio)methane</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2010-12-15</date><risdate>2010</risdate><volume>132</volume><issue>49</issue><spage>17452</spage><epage>17458</epage><pages>17452-17458</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>About 40 years have passed since methylene dizinc reagent was discovered as a substitute for Wittig reagent. Density functional theory (DFT) calculations have been performed to understand the reaction pathways of methylenation of carbonyl compounds with bis(iodozincio)methane. The present computational/theoretical study concluded that the methylenation reaction with gem-dizinc reagent proceeds as a two-step reaction, that is, methylene addition (RDS) and olefination. In the first step, the nucleophilic attack of the CH2 group enhanced by two Zn proceeds under the assistance of the electrophilic activation of the carbonyl group with the Zn atom. In the second step, the olefination is facilitated by both Zn atoms of the gem-dizinc reagent without an electron transfer process.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>21082850</pmid><doi>10.1021/ja104439w</doi><tpages>7</tpages></addata></record> |
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| source | MEDLINE; American Chemical Society Journals |
| subjects | Aldehydes - chemistry Alkenes - chemistry Carboxylic Acids - chemistry Indicators and Reagents Ketones - chemistry Methane - analogs & derivatives Methane - chemistry |
| title | Reaction Pathway of Methylenation of Carbonyl Compounds with Bis(iodozincio)methane |
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