Synthesis of 2-Hydroxy-1,4-oxazin-3-ones through Ring Transformation of 3-Hydroxy-4-(1,2-dihydroxyethyl)-β-lactams and a Study of Their Reactivity
The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to the oxidant sodium periodate was evaluated, unexpectedly resulting in the exclusive formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ri...
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| Veröffentlicht in: | Chemistry : a European journal 2013-03, Vol.19 (10), p.3383-3396 |
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| creator | Mollet, Karen Goossens, Hannelore Piens, Nicola Catak, Saron Waroquier, Michel Törnroos, Karl W. Van Speybroeck, Veronique D'hooghe, Matthias De Kimpe, Norbert |
| description | The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to the oxidant sodium periodate was evaluated, unexpectedly resulting in the exclusive formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ring expansion. This peculiar transformation stands in sharp contrast with the known NaIO4‐mediated oxidation of 3‐alkoxy‐ and 3‐phenoxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams, which exclusively leads to the corresponding 4‐formyl‐β‐lactams without a subsequent ring enlargement. In addition, this new class of functionalized oxazin‐3‐ones was further evaluated for its potential use as building blocks in the synthesis of a variety of differently substituted oxazin‐3‐ones, morpholin‐3‐ones and pyrazinones. Furthermore, additional insights into the mechanism and the factors governing this new ring‐expansion reaction were provided by means of density functional theory calculations.
Expanding horizons: The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to sodium periodate was evaluated, unexpectedly resulting in the formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ring expansion. This result is in sharp contrast to the known NaIO4‐mediated oxidation of 3‐alkoxy‐ and 3‐phenoxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams, which leads to the corresponding 4‐formyl‐β‐lactams without a subsequent ring enlargement (see scheme). |
| doi_str_mv | 10.1002/chem.201203314 |
| format | Article |
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Expanding horizons: The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to sodium periodate was evaluated, unexpectedly resulting in the formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ring expansion. This result is in sharp contrast to the known NaIO4‐mediated oxidation of 3‐alkoxy‐ and 3‐phenoxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams, which leads to the corresponding 4‐formyl‐β‐lactams without a subsequent ring enlargement (see scheme).</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201203314</identifier><identifier>PMID: 23348746</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Azetidines - chemistry ; beta-Lactams - chemical synthesis ; beta-Lactams - chemistry ; bond cleavage ; density functional calculations ; Molecular Structure ; oxazin-3-ones ; Oxazines - chemical synthesis ; Oxazines - chemistry ; Oxidation-Reduction ; Periodic Acid - chemistry ; reaction mechanisms ; ring expansion ; Stereoisomerism ; β-lactams</subject><ispartof>Chemistry : a European journal, 2013-03, Vol.19 (10), p.3383-3396</ispartof><rights>Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2984-edb3222bcf06f7b8c8836443e3ff54a669a351f3fd2b9e71f317d74e716d240a3</citedby><cites>FETCH-LOGICAL-c2984-edb3222bcf06f7b8c8836443e3ff54a669a351f3fd2b9e71f317d74e716d240a3</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%2Fchem.201203314$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201203314$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23348746$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mollet, Karen</creatorcontrib><creatorcontrib>Goossens, Hannelore</creatorcontrib><creatorcontrib>Piens, Nicola</creatorcontrib><creatorcontrib>Catak, Saron</creatorcontrib><creatorcontrib>Waroquier, Michel</creatorcontrib><creatorcontrib>Törnroos, Karl W.</creatorcontrib><creatorcontrib>Van Speybroeck, Veronique</creatorcontrib><creatorcontrib>D'hooghe, Matthias</creatorcontrib><creatorcontrib>De Kimpe, Norbert</creatorcontrib><title>Synthesis of 2-Hydroxy-1,4-oxazin-3-ones through Ring Transformation of 3-Hydroxy-4-(1,2-dihydroxyethyl)-β-lactams and a Study of Their Reactivity</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to the oxidant sodium periodate was evaluated, unexpectedly resulting in the exclusive formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ring expansion. This peculiar transformation stands in sharp contrast with the known NaIO4‐mediated oxidation of 3‐alkoxy‐ and 3‐phenoxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams, which exclusively leads to the corresponding 4‐formyl‐β‐lactams without a subsequent ring enlargement. In addition, this new class of functionalized oxazin‐3‐ones was further evaluated for its potential use as building blocks in the synthesis of a variety of differently substituted oxazin‐3‐ones, morpholin‐3‐ones and pyrazinones. Furthermore, additional insights into the mechanism and the factors governing this new ring‐expansion reaction were provided by means of density functional theory calculations.
Expanding horizons: The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to sodium periodate was evaluated, unexpectedly resulting in the formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ring expansion. This result is in sharp contrast to the known NaIO4‐mediated oxidation of 3‐alkoxy‐ and 3‐phenoxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams, which leads to the corresponding 4‐formyl‐β‐lactams without a subsequent ring enlargement (see scheme).</description><subject>Azetidines - chemistry</subject><subject>beta-Lactams - chemical synthesis</subject><subject>beta-Lactams - chemistry</subject><subject>bond cleavage</subject><subject>density functional calculations</subject><subject>Molecular Structure</subject><subject>oxazin-3-ones</subject><subject>Oxazines - chemical synthesis</subject><subject>Oxazines - chemistry</subject><subject>Oxidation-Reduction</subject><subject>Periodic Acid - chemistry</subject><subject>reaction mechanisms</subject><subject>ring expansion</subject><subject>Stereoisomerism</subject><subject>β-lactams</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkcFu1DAURS0EotPCliXKskj1YPs5drJEozKD1BbRDoKd5SR2Y0jiYid0wm_wJ3wI30RGKSN2rN7T8zl34YvQC0qWlBD2uqxNu2SEMgJA-SO0oCmjGKRIH6MFybnEIoX8CB3H-IUQkguAp-iIAfBMcrFAP2_Grq9NdDHxNmF4M1bB70ZMzzj2O_3DdRiw70xM-jr44bZOrl13m2yD7qL1odW9891ehYPK8Sk9Y7hy9XwwfT02r_DvX7jRZa_bmOiuSnRy0w_VuFe3tXEhuTbTq_vu-vEZemJ1E83zh3mCPr493642-OL9-t3qzQUuWZ5xbKoCGGNFaYmwssjKLAPBORiwNuVaiFxDSi3YihW5kdNGZSX5tImKcaLhBJ3OuXfBfxtM7FXrYmmaRnfGD1FRoEwIlko-ocsZLYOPMRir7oJrdRgVJWpfhNoXoQ5FTMLLh-yhaE11wP_-_ATkM3DvGjP-J06tNueX_4bj2XWxN7uDq8NXJSTIVH26WqsP689SXMmtuoQ_fjekuQ</recordid><startdate>20130304</startdate><enddate>20130304</enddate><creator>Mollet, Karen</creator><creator>Goossens, Hannelore</creator><creator>Piens, Nicola</creator><creator>Catak, Saron</creator><creator>Waroquier, Michel</creator><creator>Törnroos, Karl W.</creator><creator>Van Speybroeck, Veronique</creator><creator>D'hooghe, Matthias</creator><creator>De Kimpe, Norbert</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><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>20130304</creationdate><title>Synthesis of 2-Hydroxy-1,4-oxazin-3-ones through Ring Transformation of 3-Hydroxy-4-(1,2-dihydroxyethyl)-β-lactams and a Study of Their Reactivity</title><author>Mollet, Karen ; Goossens, Hannelore ; Piens, Nicola ; Catak, Saron ; Waroquier, Michel ; Törnroos, Karl W. ; Van Speybroeck, Veronique ; D'hooghe, Matthias ; De Kimpe, Norbert</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2984-edb3222bcf06f7b8c8836443e3ff54a669a351f3fd2b9e71f317d74e716d240a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Azetidines - chemistry</topic><topic>beta-Lactams - chemical synthesis</topic><topic>beta-Lactams - chemistry</topic><topic>bond cleavage</topic><topic>density functional calculations</topic><topic>Molecular Structure</topic><topic>oxazin-3-ones</topic><topic>Oxazines - chemical synthesis</topic><topic>Oxazines - chemistry</topic><topic>Oxidation-Reduction</topic><topic>Periodic Acid - chemistry</topic><topic>reaction mechanisms</topic><topic>ring expansion</topic><topic>Stereoisomerism</topic><topic>β-lactams</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mollet, Karen</creatorcontrib><creatorcontrib>Goossens, Hannelore</creatorcontrib><creatorcontrib>Piens, Nicola</creatorcontrib><creatorcontrib>Catak, Saron</creatorcontrib><creatorcontrib>Waroquier, Michel</creatorcontrib><creatorcontrib>Törnroos, Karl W.</creatorcontrib><creatorcontrib>Van Speybroeck, Veronique</creatorcontrib><creatorcontrib>D'hooghe, Matthias</creatorcontrib><creatorcontrib>De Kimpe, Norbert</creatorcontrib><collection>Istex</collection><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>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mollet, Karen</au><au>Goossens, Hannelore</au><au>Piens, Nicola</au><au>Catak, Saron</au><au>Waroquier, Michel</au><au>Törnroos, Karl W.</au><au>Van Speybroeck, Veronique</au><au>D'hooghe, Matthias</au><au>De Kimpe, Norbert</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of 2-Hydroxy-1,4-oxazin-3-ones through Ring Transformation of 3-Hydroxy-4-(1,2-dihydroxyethyl)-β-lactams and a Study of Their Reactivity</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2013-03-04</date><risdate>2013</risdate><volume>19</volume><issue>10</issue><spage>3383</spage><epage>3396</epage><pages>3383-3396</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to the oxidant sodium periodate was evaluated, unexpectedly resulting in the exclusive formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ring expansion. This peculiar transformation stands in sharp contrast with the known NaIO4‐mediated oxidation of 3‐alkoxy‐ and 3‐phenoxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams, which exclusively leads to the corresponding 4‐formyl‐β‐lactams without a subsequent ring enlargement. In addition, this new class of functionalized oxazin‐3‐ones was further evaluated for its potential use as building blocks in the synthesis of a variety of differently substituted oxazin‐3‐ones, morpholin‐3‐ones and pyrazinones. Furthermore, additional insights into the mechanism and the factors governing this new ring‐expansion reaction were provided by means of density functional theory calculations.
Expanding horizons: The reactivity of 3‐hydroxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams with regard to sodium periodate was evaluated, unexpectedly resulting in the formation of new 2‐hydroxy‐1,4‐oxazin‐3‐ones through a C3C4 bond cleavage of the intermediate 4‐formyl‐3‐hydroxy‐β‐lactams followed by a ring expansion. This result is in sharp contrast to the known NaIO4‐mediated oxidation of 3‐alkoxy‐ and 3‐phenoxy‐4‐(1,2‐dihydroxyethyl)‐β‐lactams, which leads to the corresponding 4‐formyl‐β‐lactams without a subsequent ring enlargement (see scheme).</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>23348746</pmid><doi>10.1002/chem.201203314</doi><tpages>14</tpages></addata></record> |
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| subjects | Azetidines - chemistry beta-Lactams - chemical synthesis beta-Lactams - chemistry bond cleavage density functional calculations Molecular Structure oxazin-3-ones Oxazines - chemical synthesis Oxazines - chemistry Oxidation-Reduction Periodic Acid - chemistry reaction mechanisms ring expansion Stereoisomerism β-lactams |
| title | Synthesis of 2-Hydroxy-1,4-oxazin-3-ones through Ring Transformation of 3-Hydroxy-4-(1,2-dihydroxyethyl)-β-lactams and a Study of Their Reactivity |
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