Phosphine-catalyzed Michael additions to α-methylene-γ-butyrolactones
The highly efficient addition of phosphorus and carbon pronucleophiles to α-methylene-γ-butyrolactones (tulipalin A and arglabin) under n -Bu 3 P catalysis is reported. Kinetic experiments indicate that the unprecedentedly high reactivity of α-methylene-γ-butyrolactones results from the rigid s- cis...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2019-08, Vol.17 (31), p.7293-7299 |
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| creator | Salin, Alexey V Islamov, Daut R |
| description | The highly efficient addition of phosphorus and carbon pronucleophiles to α-methylene-γ-butyrolactones (tulipalin A and arglabin) under
n
-Bu
3
P catalysis is reported. Kinetic experiments indicate that the unprecedentedly high reactivity of α-methylene-γ-butyrolactones results from the rigid s-
cis
geometry of the 1-oxa-1,3-butadiene moiety that favors generation of zwitterionic intermediate stabilized by interaction between the phosphonium center and adjacent carbonyl oxygen. The presented strategy offers an economical and practical method for functionalization of natural biologically active α-methylene-γ-butyrolactones with high levels of chemo- and stereoselectivity.
Increased reactivity of α-methylene-γ-butyrolactones towards tertiary phosphines is reported; this effect is used to improve the efficiency of phosphine-catalyzed reactions. |
| doi_str_mv | 10.1039/c9ob01401b |
| format | Article |
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n
-Bu
3
P catalysis is reported. Kinetic experiments indicate that the unprecedentedly high reactivity of α-methylene-γ-butyrolactones results from the rigid s-
cis
geometry of the 1-oxa-1,3-butadiene moiety that favors generation of zwitterionic intermediate stabilized by interaction between the phosphonium center and adjacent carbonyl oxygen. The presented strategy offers an economical and practical method for functionalization of natural biologically active α-methylene-γ-butyrolactones with high levels of chemo- and stereoselectivity.
Increased reactivity of α-methylene-γ-butyrolactones towards tertiary phosphines is reported; this effect is used to improve the efficiency of phosphine-catalyzed reactions.</description><identifier>ISSN: 1477-0520</identifier><identifier>EISSN: 1477-0539</identifier><identifier>DOI: 10.1039/c9ob01401b</identifier><identifier>PMID: 31328762</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>1,3-Butadiene ; Biological activity ; Butadiene ; Butyrolactone ; Carbonyl compounds ; Carbonyls ; Catalysis ; Crystallography ; Methylene ; Phosphine ; Phosphorus ; Stereoselectivity</subject><ispartof>Organic & biomolecular chemistry, 2019-08, Vol.17 (31), p.7293-7299</ispartof><rights>Copyright Royal Society of Chemistry 2019</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c337t-43f1ff596e10de6fdc49dd0bc083885d3540c8da09846ef5f3292921c36a1ca43</citedby><cites>FETCH-LOGICAL-c337t-43f1ff596e10de6fdc49dd0bc083885d3540c8da09846ef5f3292921c36a1ca43</cites><orcidid>0000-0002-2751-1666</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31328762$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Salin, Alexey V</creatorcontrib><creatorcontrib>Islamov, Daut R</creatorcontrib><title>Phosphine-catalyzed Michael additions to α-methylene-γ-butyrolactones</title><title>Organic & biomolecular chemistry</title><addtitle>Org Biomol Chem</addtitle><description>The highly efficient addition of phosphorus and carbon pronucleophiles to α-methylene-γ-butyrolactones (tulipalin A and arglabin) under
n
-Bu
3
P catalysis is reported. Kinetic experiments indicate that the unprecedentedly high reactivity of α-methylene-γ-butyrolactones results from the rigid s-
cis
geometry of the 1-oxa-1,3-butadiene moiety that favors generation of zwitterionic intermediate stabilized by interaction between the phosphonium center and adjacent carbonyl oxygen. The presented strategy offers an economical and practical method for functionalization of natural biologically active α-methylene-γ-butyrolactones with high levels of chemo- and stereoselectivity.
Increased reactivity of α-methylene-γ-butyrolactones towards tertiary phosphines is reported; this effect is used to improve the efficiency of phosphine-catalyzed reactions.</description><subject>1,3-Butadiene</subject><subject>Biological activity</subject><subject>Butadiene</subject><subject>Butyrolactone</subject><subject>Carbonyl compounds</subject><subject>Carbonyls</subject><subject>Catalysis</subject><subject>Crystallography</subject><subject>Methylene</subject><subject>Phosphine</subject><subject>Phosphorus</subject><subject>Stereoselectivity</subject><issn>1477-0520</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpd0c9LwzAUB_AgipvTi3dl4EWEatKkaXJ0Q6egzIOeS5oftKNtZpMe6n8l_h_7m8zcnCA5vEA-PN77BoBTBK8RxPxGcptDRCDK98AQkTSNYIL5_u4ewwE4cm4BIeIpJYdggBGOWUrjIZi9FNYti7LRkRReVP2HVuPnUhZCV2OhVOlL27ixt-PVZ1RrX_SVDnb1FeWd71tbCelto90xODCicvpkW0fg7f7udfoQPc1nj9Pbp0hinPqIYIOMSTjVCCpNjZKEKwVzCRlmLFE4IVAyJSBnhGqTGBzzcJDEVCApCB6By03fZWvfO-18VpdO6qoSjbady-KYhiUJjWmgF__ownZtE6ZbK8YZwjwJ6mqjZGuda7XJlm1Zi7bPEMzW8WZTPp_8xDsJ-HzbsstrrXb0N88AzjagdXL3-vc_-BvY3X_A</recordid><startdate>20190807</startdate><enddate>20190807</enddate><creator>Salin, Alexey V</creator><creator>Islamov, Daut R</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QO</scope><scope>7T7</scope><scope>7TM</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>P64</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-2751-1666</orcidid></search><sort><creationdate>20190807</creationdate><title>Phosphine-catalyzed Michael additions to α-methylene-γ-butyrolactones</title><author>Salin, Alexey V ; Islamov, Daut R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c337t-43f1ff596e10de6fdc49dd0bc083885d3540c8da09846ef5f3292921c36a1ca43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>1,3-Butadiene</topic><topic>Biological activity</topic><topic>Butadiene</topic><topic>Butyrolactone</topic><topic>Carbonyl compounds</topic><topic>Carbonyls</topic><topic>Catalysis</topic><topic>Crystallography</topic><topic>Methylene</topic><topic>Phosphine</topic><topic>Phosphorus</topic><topic>Stereoselectivity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Salin, Alexey V</creatorcontrib><creatorcontrib>Islamov, Daut R</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Biotechnology Research Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Nucleic Acids Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Organic & biomolecular chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Salin, Alexey V</au><au>Islamov, Daut R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Phosphine-catalyzed Michael additions to α-methylene-γ-butyrolactones</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2019-08-07</date><risdate>2019</risdate><volume>17</volume><issue>31</issue><spage>7293</spage><epage>7299</epage><pages>7293-7299</pages><issn>1477-0520</issn><eissn>1477-0539</eissn><abstract>The highly efficient addition of phosphorus and carbon pronucleophiles to α-methylene-γ-butyrolactones (tulipalin A and arglabin) under
n
-Bu
3
P catalysis is reported. Kinetic experiments indicate that the unprecedentedly high reactivity of α-methylene-γ-butyrolactones results from the rigid s-
cis
geometry of the 1-oxa-1,3-butadiene moiety that favors generation of zwitterionic intermediate stabilized by interaction between the phosphonium center and adjacent carbonyl oxygen. The presented strategy offers an economical and practical method for functionalization of natural biologically active α-methylene-γ-butyrolactones with high levels of chemo- and stereoselectivity.
Increased reactivity of α-methylene-γ-butyrolactones towards tertiary phosphines is reported; this effect is used to improve the efficiency of phosphine-catalyzed reactions.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>31328762</pmid><doi>10.1039/c9ob01401b</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-2751-1666</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-0520 |
| ispartof | Organic & biomolecular chemistry, 2019-08, Vol.17 (31), p.7293-7299 |
| issn | 1477-0520 1477-0539 |
| language | eng |
| recordid | cdi_proquest_journals_2268981395 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | 1,3-Butadiene Biological activity Butadiene Butyrolactone Carbonyl compounds Carbonyls Catalysis Crystallography Methylene Phosphine Phosphorus Stereoselectivity |
| title | Phosphine-catalyzed Michael additions to α-methylene-γ-butyrolactones |
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