Synthesis of 2-Alkylidenecyclopentanones via Palladium-Catalyzed Carbopalladation/Ring Expansion of 1-(1-Alkynyl)cyclobutanols

Synthesis of 2-Alkylidenecyclopentanones via Palladium-Catalyzed Carbopalladation/Ring Expansion of 1-(1-Alkynyl)cyclobutanols

The palladium-catalyzed cross-coupling of aryl halides or vinylic halides or triflates and 1-(1-alkynyl)cyclobutanols affords good yields of stereoisomerically pure 2-arylidene- or 2-(2-alkenylidene)cyclopentanones, respectively. The process involves (1) oxidative addition of the organic halide or t...

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Veröffentlicht in:Journal of organic chemistry 2002-04, Vol.67 (7), p.2027-2033
Hauptverfasser: Larock, Richard C, Reddy, Ch. Kishan
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Alicyclic compounds
Alicyclic compounds, terpenoids, prostaglandins, steroids
Chemistry
Exact sciences and technology
Organic chemistry
Preparations and properties
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container_issue 7
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container_title Journal of organic chemistry
container_volume 67
creator Larock, Richard C
Reddy, Ch. Kishan
description The palladium-catalyzed cross-coupling of aryl halides or vinylic halides or triflates and 1-(1-alkynyl)cyclobutanols affords good yields of stereoisomerically pure 2-arylidene- or 2-(2-alkenylidene)cyclopentanones, respectively. The process involves (1) oxidative addition of the organic halide or triflate to Pd(0), (2) regioselective, intermolecular carbopalladation of the carbon−carbon triple bond of the 1-(1-alkynyl)cyclobutanol to produce a vinylic palladium intermediate, (3) regioselective ring expansion to a palladacycle, and (4) reductive elimination of the 2-alkylidenecyclopentanone with simultaneous regeneration of the Pd(0) catalyst. Generally, the best results are obtained by employing 10 mol % of Pd(OAc)2, 20 mol % of PPh3, 2 equiv of the aryl or vinylic iodide or vinylic triflate, 2 equiv of diisopropylethylamine, and n-Bu4NCl in DMF as the solvent.
doi_str_mv 10.1021/jo010577e
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Generally, the best results are obtained by employing 10 mol % of Pd(OAc)2, 20 mol % of PPh3, 2 equiv of the aryl or vinylic iodide or vinylic triflate, 2 equiv of diisopropylethylamine, and n-Bu4NCl in DMF as the solvent.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo010577e</identifier><identifier>PMID: 11925206</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Alicyclic compounds ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; Chemistry ; Exact sciences and technology ; Organic chemistry ; Preparations and properties</subject><ispartof>Journal of organic chemistry, 2002-04, Vol.67 (7), p.2027-2033</ispartof><rights>Copyright © 2002 American Chemical Society</rights><rights>2002 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a379t-cc3c1455eaabe9c11ec16e290a63dee0d1e640f2a1857c50ee53b892e5acc3163</citedby><cites>FETCH-LOGICAL-a379t-cc3c1455eaabe9c11ec16e290a63dee0d1e640f2a1857c50ee53b892e5acc3163</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/jo010577e$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo010577e$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&amp;idt=13600532$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11925206$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Larock, Richard C</creatorcontrib><creatorcontrib>Reddy, Ch. Kishan</creatorcontrib><title>Synthesis of 2-Alkylidenecyclopentanones via Palladium-Catalyzed Carbopalladation/Ring Expansion of 1-(1-Alkynyl)cyclobutanols</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>The palladium-catalyzed cross-coupling of aryl halides or vinylic halides or triflates and 1-(1-alkynyl)cyclobutanols affords good yields of stereoisomerically pure 2-arylidene- or 2-(2-alkenylidene)cyclopentanones, respectively. The process involves (1) oxidative addition of the organic halide or triflate to Pd(0), (2) regioselective, intermolecular carbopalladation of the carbon−carbon triple bond of the 1-(1-alkynyl)cyclobutanol to produce a vinylic palladium intermediate, (3) regioselective ring expansion to a palladacycle, and (4) reductive elimination of the 2-alkylidenecyclopentanone with simultaneous regeneration of the Pd(0) catalyst. Generally, the best results are obtained by employing 10 mol % of Pd(OAc)2, 20 mol % of PPh3, 2 equiv of the aryl or vinylic iodide or vinylic triflate, 2 equiv of diisopropylethylamine, and n-Bu4NCl in DMF as the solvent.</description><subject>Alicyclic compounds</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><recordid>eNptkc1u1DAUhS1ERYfCghdA2YDoItQ_Y6dZVkOhlQqMaJHYWTfODbj12KmdoIYFz47nR50N3ljW_fzp6FxCXjH6nlHOTm4DZVRWFT4hMyY5LVVN50_JjFLOS8GVOCTPU7ql-Ugpn5FDxmqeOTUjf68nP_zCZFMRuoKXZ-5ucrZFj2YyLvToB_DBYyp-WyiW4By0dlyVCxjATX-wLRYQm9BvBjDY4E--Wf-zOH_owaf8XGtZ-Y5tzH5yxxtvM661Lr0gBx24hC939xH5_vH8ZnFRXn39dLk4uypBVPVQGiMMm0uJAA3WhjE0TCGvKSjRItKWoZrTjgM7lZWRFFGK5rTmKCF_ZUockbdbbx_D_Yhp0CubDObQHsOYdMWkrOhcZPB4C5oYUorY6T7aFcRJM6rXZevHsjP7eicdmxW2e3LXbgbe7ABIBlwXwRub9pxQeSGCZ67ccjYN-PA4h3inVSUqqW-W1_rDZ7H8cqFq_WPvBZNynjH63N1_Av4Dc_ukKw</recordid><startdate>20020405</startdate><enddate>20020405</enddate><creator>Larock, Richard C</creator><creator>Reddy, Ch. 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Kishan</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a379t-cc3c1455eaabe9c11ec16e290a63dee0d1e640f2a1857c50ee53b892e5acc3163</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>Alicyclic compounds</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Larock, Richard C</creatorcontrib><creatorcontrib>Reddy, Ch. Kishan</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Larock, Richard C</au><au>Reddy, Ch. Kishan</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of 2-Alkylidenecyclopentanones via Palladium-Catalyzed Carbopalladation/Ring Expansion of 1-(1-Alkynyl)cyclobutanols</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. 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Generally, the best results are obtained by employing 10 mol % of Pd(OAc)2, 20 mol % of PPh3, 2 equiv of the aryl or vinylic iodide or vinylic triflate, 2 equiv of diisopropylethylamine, and n-Bu4NCl in DMF as the solvent.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>11925206</pmid><doi>10.1021/jo010577e</doi><tpages>7</tpages></addata></record>
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source American Chemical Society Journals
subjects Alicyclic compounds
Alicyclic compounds, terpenoids, prostaglandins, steroids
Chemistry
Exact sciences and technology
Organic chemistry
Preparations and properties
title Synthesis of 2-Alkylidenecyclopentanones via Palladium-Catalyzed Carbopalladation/Ring Expansion of 1-(1-Alkynyl)cyclobutanols
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