Periselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and N -(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study
The thermal 6π aza-Diels-Alder cycloadditions between α-oxoketenes, derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and -(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the...
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Veröffentlicht in: | Journal of organic chemistry 2020-06, Vol.85 (11), p.7368-7377 |
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creator | Castillo, Juan-Carlos Castro Agudelo, Brian Gálvez, Jaime Carissan, Yannick Rodriguez, Jean Coquerel, Yoann |
description | The thermal 6π aza-Diels-Alder cycloadditions between α-oxoketenes,
derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and
-(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the α-oxoketenes involved. For instance, cyclic five-membered α-oxoketenes lead preferentially to spiro hydropyridin-4-ones, which involves the α-oxoketenes as the 2π partners at their C═C double bond and the
-(5-pyrazolyl)imines as the 4π partners at their 2-azadiene moiety. In contrast, other cyclic and acyclic α-oxoketenes lead preferentially to 1,3-oxazin-4-ones, which now involves the α-oxoketenes as the 4π partners at their 1-oxadiene moiety and the
-(5-pyrazolyl)imines as the 2π partners at their C═N double bond. A computational modeling study using DFT methods allowed rationalizing this change of periselectivity: the formation of spiro hydropyridin-4-ones is under thermodynamic control while the formation of 1,3-oxazin-4-ones is kinetically controlled, and slightly thermodynamically disfavored in the five-membered ring series. The competing cyclodimerization of the α-oxoketenes is also studied in detail. |
doi_str_mv | 10.1021/acs.joc.0c00767 |
format | Article |
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derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and
-(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the α-oxoketenes involved. For instance, cyclic five-membered α-oxoketenes lead preferentially to spiro hydropyridin-4-ones, which involves the α-oxoketenes as the 2π partners at their C═C double bond and the
-(5-pyrazolyl)imines as the 4π partners at their 2-azadiene moiety. In contrast, other cyclic and acyclic α-oxoketenes lead preferentially to 1,3-oxazin-4-ones, which now involves the α-oxoketenes as the 4π partners at their 1-oxadiene moiety and the
-(5-pyrazolyl)imines as the 2π partners at their C═N double bond. A computational modeling study using DFT methods allowed rationalizing this change of periselectivity: the formation of spiro hydropyridin-4-ones is under thermodynamic control while the formation of 1,3-oxazin-4-ones is kinetically controlled, and slightly thermodynamically disfavored in the five-membered ring series. The competing cyclodimerization of the α-oxoketenes is also studied in detail.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/acs.joc.0c00767</identifier><identifier>PMID: 32396353</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Chemical Sciences ; Organic chemistry</subject><ispartof>Journal of organic chemistry, 2020-06, Vol.85 (11), p.7368-7377</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c372t-c2f95a70a7d100ec19296b5558647763add9b2a0362002683b9643f53945e8913</citedby><cites>FETCH-LOGICAL-c372t-c2f95a70a7d100ec19296b5558647763add9b2a0362002683b9643f53945e8913</cites><orcidid>0000-0002-9876-0272 ; 0000-0003-0646-006X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,2752,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/32396353$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-02990649$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Castillo, Juan-Carlos</creatorcontrib><creatorcontrib>Castro Agudelo, Brian</creatorcontrib><creatorcontrib>Gálvez, Jaime</creatorcontrib><creatorcontrib>Carissan, Yannick</creatorcontrib><creatorcontrib>Rodriguez, Jean</creatorcontrib><creatorcontrib>Coquerel, Yoann</creatorcontrib><title>Periselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and N -(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study</title><title>Journal of organic chemistry</title><addtitle>J Org Chem</addtitle><description>The thermal 6π aza-Diels-Alder cycloadditions between α-oxoketenes,
derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and
-(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the α-oxoketenes involved. For instance, cyclic five-membered α-oxoketenes lead preferentially to spiro hydropyridin-4-ones, which involves the α-oxoketenes as the 2π partners at their C═C double bond and the
-(5-pyrazolyl)imines as the 4π partners at their 2-azadiene moiety. In contrast, other cyclic and acyclic α-oxoketenes lead preferentially to 1,3-oxazin-4-ones, which now involves the α-oxoketenes as the 4π partners at their 1-oxadiene moiety and the
-(5-pyrazolyl)imines as the 2π partners at their C═N double bond. A computational modeling study using DFT methods allowed rationalizing this change of periselectivity: the formation of spiro hydropyridin-4-ones is under thermodynamic control while the formation of 1,3-oxazin-4-ones is kinetically controlled, and slightly thermodynamically disfavored in the five-membered ring series. The competing cyclodimerization of the α-oxoketenes is also studied in detail.</description><subject>Chemical Sciences</subject><subject>Organic chemistry</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNo9kcFuGyEQhlHUKnHTnHurOCYHnFnYZU1vlps2lawmUpMzYtmxTMou7oLTbJ6jL9IX6TMV1264DAP__MzwEfKugGkBvLg0Nk4fgp2CBahlfUQmRcWBSQXlKzIB4JwJLsUJeRPjA-RVVdUxORFcKCkqMSG_bnFwET3a5B5dGqnraVojNc-GfXToI5v7Fge6GK0Ppm1dcqGnDaafiD3985vdPIXvmLDHSE3f0q-UnVfsdhzMc_Cjv3Cdy1cf6JwuQtfkfUuvnjb5zQ77ZPy_mrs1hgGTszn_lrbt-Ja8Xhkf8ewQT8n9p6u7xTVb3nz-spgvmRU1T8zylapMDaZuCwC0heJKNnnCmSzrWorcrmq4ASF5_gk5E42SpVhVQpUVzlQhTsnF3ndtvN7knsww6mCcvp4v9e4MuFIgS_W4057vtZsh_NhiTLpz0aL3psewjZqXwMuSQwlZermX2iHEOODqxbsAvcOmMzadsekDtlzx_mC-bTpsX_T_OYm_uQ-Ukg</recordid><startdate>20200605</startdate><enddate>20200605</enddate><creator>Castillo, Juan-Carlos</creator><creator>Castro Agudelo, Brian</creator><creator>Gálvez, Jaime</creator><creator>Carissan, Yannick</creator><creator>Rodriguez, Jean</creator><creator>Coquerel, Yoann</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>1XC</scope><scope>VOOES</scope><orcidid>https://orcid.org/0000-0002-9876-0272</orcidid><orcidid>https://orcid.org/0000-0003-0646-006X</orcidid></search><sort><creationdate>20200605</creationdate><title>Periselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and N -(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study</title><author>Castillo, Juan-Carlos ; Castro Agudelo, Brian ; Gálvez, Jaime ; Carissan, Yannick ; Rodriguez, Jean ; Coquerel, Yoann</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c372t-c2f95a70a7d100ec19296b5558647763add9b2a0362002683b9643f53945e8913</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Chemical Sciences</topic><topic>Organic chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Castillo, Juan-Carlos</creatorcontrib><creatorcontrib>Castro Agudelo, Brian</creatorcontrib><creatorcontrib>Gálvez, Jaime</creatorcontrib><creatorcontrib>Carissan, Yannick</creatorcontrib><creatorcontrib>Rodriguez, Jean</creatorcontrib><creatorcontrib>Coquerel, Yoann</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Castillo, Juan-Carlos</au><au>Castro Agudelo, Brian</au><au>Gálvez, Jaime</au><au>Carissan, Yannick</au><au>Rodriguez, Jean</au><au>Coquerel, Yoann</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Periselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and N -(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J Org Chem</addtitle><date>2020-06-05</date><risdate>2020</risdate><volume>85</volume><issue>11</issue><spage>7368</spage><epage>7377</epage><pages>7368-7377</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>The thermal 6π aza-Diels-Alder cycloadditions between α-oxoketenes,
derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and
-(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the α-oxoketenes involved. For instance, cyclic five-membered α-oxoketenes lead preferentially to spiro hydropyridin-4-ones, which involves the α-oxoketenes as the 2π partners at their C═C double bond and the
-(5-pyrazolyl)imines as the 4π partners at their 2-azadiene moiety. In contrast, other cyclic and acyclic α-oxoketenes lead preferentially to 1,3-oxazin-4-ones, which now involves the α-oxoketenes as the 4π partners at their 1-oxadiene moiety and the
-(5-pyrazolyl)imines as the 2π partners at their C═N double bond. A computational modeling study using DFT methods allowed rationalizing this change of periselectivity: the formation of spiro hydropyridin-4-ones is under thermodynamic control while the formation of 1,3-oxazin-4-ones is kinetically controlled, and slightly thermodynamically disfavored in the five-membered ring series. The competing cyclodimerization of the α-oxoketenes is also studied in detail.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>32396353</pmid><doi>10.1021/acs.joc.0c00767</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0002-9876-0272</orcidid><orcidid>https://orcid.org/0000-0003-0646-006X</orcidid><oa>free_for_read</oa></addata></record> |
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title | Periselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and N -(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study |
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