The Hetero-Diels-Alder Addition of Sulfur Dioxide to 1-Fluorobuta-1,3-dienes: The Sofa Conformations Preferred by 6-Fluorosultines (6-Fluoro-3,6-dihydro-1,2-oxathiin-2-oxides) Enjoy Enthalpic and Conformational Anomeric Effects
The reactivity of (E)‐ and (Z)‐1‐fluorobuta‐1,3‐diene ((E)‐ and (Z)‐11), 2‐fluorobutadiene (12), (E)‐ and (Z)‐1‐(fluoromethylidene)‐2‐methylidenecyclohexane ((E)‐ and (Z)‐13) toward SO2 has been explored and compared with that of (Z)‐ and (E)‐1‐(fluoromethylidene)‐2‐methylidene‐3,4‐dihydronaphthalen...
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| Veröffentlicht in: | Chemistry : a European journal 2002-03, Vol.8 (6), p.1336-1355 |
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| creator | Roversi, Elena Scopelliti, Rosario Solari, Euro Estoppey, Raphaël Vogel, Pierre Braña, Pedro Menéndez, Bibiana Sordo, José A. |
| description | The reactivity of (E)‐ and (Z)‐1‐fluorobuta‐1,3‐diene ((E)‐ and (Z)‐11), 2‐fluorobutadiene (12), (E)‐ and (Z)‐1‐(fluoromethylidene)‐2‐methylidenecyclohexane ((E)‐ and (Z)‐13) toward SO2 has been explored and compared with that of (Z)‐ and (E)‐1‐(fluoromethylidene)‐2‐methylidene‐3,4‐dihydronaphthalene ((Z)‐8 and (E)‐8). In agreement with quantum calculations, 12 is unreactive toward SO2 (no cycloaddition, only polymerization), whereas (E)‐1‐fluoro‐1,3‐dienes react more rapidly than their (Z)‐isomers to give the corresponding 6‐fluorosultines following the endo (Alder rule) mode of hetero‐Diels–Alder addition. No sulfolene has been observed following the cheletropic mode of addition with the fluorodienes, in contrast to other substituted dienes. In agreement with the calculations, cis‐2‐fluoro‐3,4‐oxathiabenzobicyclo[4.4.0]dec‐1(6),9‐diene‐4‐oxide (cis‐9, the sultine obtained by SO2 addition to (Z)‐8 under conditions of kinetic control) adopts a sofa conformation with the oxygen atom of the ring lying in the average plane of the four carbon atoms of its sultine moiety when it is in the crystalline state at −100 °C. A similar sofa conformation was found for its trans‐isomer, trans‐9, obtained by isomerization of cis‐9 or by hetero‐Diels–Alder addition of SO2 to (E)‐8. Experiments (equilibrium constant for hetero‐Diels–Alder additions, bond lengths, and bond angles in crystalline fluorosultines cis‐9 and trans‐9) and high‐level quantum calculations on cis‐ and trans‐6‐fluoro‐3,6‐dihydro‐1,2‐oxathiin‐2‐oxide (cis‐ and trans‐20) confirm the existence of a stabilizing, enthalpic, anomeric (gem‐disubstitution by sulfinyloxy and fluoro groups) effect, which is interpreted in terms of (lone pair) n(O1)→σ*(C−F) hyperconjugative interactions. This effect is strongest in the sofa conformers with a gauche arrangement of the σ(O1,S2) and σ(C6,F) bonds. The calculations suggest also that n(O1)→σ*(S2,O2′), π*(S=O), and n(S2)→σ*(O1,C6) interactions intervene and affect the relative stability of the conformers (sofa, boat, pseudo‐chair) found for 6‐fluorosultines cis‐ and trans‐20.
La réactivité du SO2 face aux (E)‐ et (Z)‐1‐fluorobuta‐1,3‐diène ((E)‐ et (Z)‐11), 2‐fluorobuta‐1,3‐diène (12), (E) et (Z)‐1‐(fluorométhylidène)‐2‐méthylidènecyclohexane ((E)‐ et (Z)‐13) est étudiée et comparée avec celle du SO2 sur le (Z)‐ et (E)‐1‐(fluorométhylidène)‐2‐méthylidène‐3,4‐dihydronaphthalène ((Z)‐ and (E)‐8). En concordance avec des calculs quantiques de haut niveau (pseudo‐G3), 12 n |
| doi_str_mv | 10.1002/1521-3765(20020315)8:6<1336::AID-CHEM1336>3.0.CO;2-R |
| format | Article |
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La réactivité du SO2 face aux (E)‐ et (Z)‐1‐fluorobuta‐1,3‐diène ((E)‐ et (Z)‐11), 2‐fluorobuta‐1,3‐diène (12), (E) et (Z)‐1‐(fluorométhylidène)‐2‐méthylidènecyclohexane ((E)‐ et (Z)‐13) est étudiée et comparée avec celle du SO2 sur le (Z)‐ et (E)‐1‐(fluorométhylidène)‐2‐méthylidène‐3,4‐dihydronaphthalène ((Z)‐ and (E)‐8). En concordance avec des calculs quantiques de haut niveau (pseudo‐G3), 12 ne réagit pas avec le SO2 en dehors de sa polymérisation (pas de cycloaddition) alors que les (E)‐1‐fluoro‐1,3‐diènes s'additionnent au SO2 plus rapidement que leurs isomères (Z) en donnant des 6‐fluorosultines. Ces additions du type hétéro‐Diels–Alder suivent la règle (endo) d'Alder. En accord avec les calculs quantiques, le 4‐oxide de cis‐2‐fluoro‐3,4‐oxathiabenzobicyclo[4.4.0]dec‐1‐(6),9‐diène (cis‐9, la sultine résultant de l'addition hetero‐Diels–Alder du SO2 sur (Z)‐8 sous conditions de contrôle cinétique) adopte une conformation sofa avec l'atome d'oxygène cyclique se plaçant dans le plan moyen des quatre atomes de carbone de l'entité sultine, à l'état cristallin à −100 °C. Une conformation sofa similaire est observée à l'état cristallin de l'isomère trans‐9, obtenu par isomérisation de cis‐9 ou par addition selon Diels–Alder du SO2 sur (E)‐8. L'expérience (constantes d'équilibre pour les additions hétéro‐Diels–Alder, les longueurs de liaisons et les angles de liaisons pour les fluorosultines crystallisées cis‐9 et trans‐9) et les calculs quantiques sur les 2‐oxydes de cis‐ et trans‐6‐fluoro‐3,6‐dihydro‐1,2‐oxathiine (cis‐20 and trans‐20) confirment l'existence d'un effet anomère enthalpique (effet de gem‐disubstitution par les groupements sulfinyloxy et fluoro) stabilisant et d'effets anomères conformationels qui sont dominés par une interaction hyperconjugative du type n(O1)→σ*(C−F). Cet effet est le plus marqué dans les conformères sofa où les liaisons σ(O1,S2) et σ(C6,F) sont gauches. Les calculs suggèrent encore que des interactions du type n(O1)→σ*(S2,O2′), π*(S=O) et n(S2)→σ*(O1,C6) interviennent également et affectent la stabilité relative des conformères sofa, bateau et pseudo‐chaise que l'on trouve sur l'hypersurface d'énergie des 6‐fluorosultines cis‐20 et trans‐20.
Unlike other 1‐halodienes, 1‐fluorodienes can undergo hetero‐Diels–Alder addition with SO2. In agreement with quantum calculations, the (E) isomers react more rapidly than the (Z) and tend to undergo the endo (Alder rule) mode of cycloaddition to give fluorosultines, as per the scheme, rather than undergoing cheletropic additions to give fluorosulfolenes. Experiments and high‐level quantum calculations on the sultines confirm the existence of stabilizing enthalpic anomeric effects, which can be interpreted in terms of n(O1)→σ*(C−F) hyperconjugative interaction. This effect is strongest in the sofa conformer, which has the oxygen atom of the ring lying in the average plane of the four carbon atoms.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/1521-3765(20020315)8:6<1336::AID-CHEM1336>3.0.CO;2-R</identifier><identifier>PMID: 11921217</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag GmbH</publisher><subject>anomeric effects ; conformation analysis ; cycloaddition ; heterocycles ; quantum calculations</subject><ispartof>Chemistry : a European journal, 2002-03, Vol.8 (6), p.1336-1355</ispartof><rights>2002 WILEY‐VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c4046-172f20614ac00227fae5b4ccb3131ca42a5b54a56f6a92a63a4f52dd7bf0b77d3</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%2F1521-3765%2820020315%298%3A6%3C1336%3A%3AAID-CHEM1336%3E3.0.CO%3B2-R$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2F1521-3765%2820020315%298%3A6%3C1336%3A%3AAID-CHEM1336%3E3.0.CO%3B2-R$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11921217$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Roversi, Elena</creatorcontrib><creatorcontrib>Scopelliti, Rosario</creatorcontrib><creatorcontrib>Solari, Euro</creatorcontrib><creatorcontrib>Estoppey, Raphaël</creatorcontrib><creatorcontrib>Vogel, Pierre</creatorcontrib><creatorcontrib>Braña, Pedro</creatorcontrib><creatorcontrib>Menéndez, Bibiana</creatorcontrib><creatorcontrib>Sordo, José A.</creatorcontrib><title>The Hetero-Diels-Alder Addition of Sulfur Dioxide to 1-Fluorobuta-1,3-dienes: The Sofa Conformations Preferred by 6-Fluorosultines (6-Fluoro-3,6-dihydro-1,2-oxathiin-2-oxides) Enjoy Enthalpic and Conformational Anomeric Effects</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>The reactivity of (E)‐ and (Z)‐1‐fluorobuta‐1,3‐diene ((E)‐ and (Z)‐11), 2‐fluorobutadiene (12), (E)‐ and (Z)‐1‐(fluoromethylidene)‐2‐methylidenecyclohexane ((E)‐ and (Z)‐13) toward SO2 has been explored and compared with that of (Z)‐ and (E)‐1‐(fluoromethylidene)‐2‐methylidene‐3,4‐dihydronaphthalene ((Z)‐8 and (E)‐8). In agreement with quantum calculations, 12 is unreactive toward SO2 (no cycloaddition, only polymerization), whereas (E)‐1‐fluoro‐1,3‐dienes react more rapidly than their (Z)‐isomers to give the corresponding 6‐fluorosultines following the endo (Alder rule) mode of hetero‐Diels–Alder addition. No sulfolene has been observed following the cheletropic mode of addition with the fluorodienes, in contrast to other substituted dienes. In agreement with the calculations, cis‐2‐fluoro‐3,4‐oxathiabenzobicyclo[4.4.0]dec‐1(6),9‐diene‐4‐oxide (cis‐9, the sultine obtained by SO2 addition to (Z)‐8 under conditions of kinetic control) adopts a sofa conformation with the oxygen atom of the ring lying in the average plane of the four carbon atoms of its sultine moiety when it is in the crystalline state at −100 °C. A similar sofa conformation was found for its trans‐isomer, trans‐9, obtained by isomerization of cis‐9 or by hetero‐Diels–Alder addition of SO2 to (E)‐8. Experiments (equilibrium constant for hetero‐Diels–Alder additions, bond lengths, and bond angles in crystalline fluorosultines cis‐9 and trans‐9) and high‐level quantum calculations on cis‐ and trans‐6‐fluoro‐3,6‐dihydro‐1,2‐oxathiin‐2‐oxide (cis‐ and trans‐20) confirm the existence of a stabilizing, enthalpic, anomeric (gem‐disubstitution by sulfinyloxy and fluoro groups) effect, which is interpreted in terms of (lone pair) n(O1)→σ*(C−F) hyperconjugative interactions. This effect is strongest in the sofa conformers with a gauche arrangement of the σ(O1,S2) and σ(C6,F) bonds. The calculations suggest also that n(O1)→σ*(S2,O2′), π*(S=O), and n(S2)→σ*(O1,C6) interactions intervene and affect the relative stability of the conformers (sofa, boat, pseudo‐chair) found for 6‐fluorosultines cis‐ and trans‐20.
La réactivité du SO2 face aux (E)‐ et (Z)‐1‐fluorobuta‐1,3‐diène ((E)‐ et (Z)‐11), 2‐fluorobuta‐1,3‐diène (12), (E) et (Z)‐1‐(fluorométhylidène)‐2‐méthylidènecyclohexane ((E)‐ et (Z)‐13) est étudiée et comparée avec celle du SO2 sur le (Z)‐ et (E)‐1‐(fluorométhylidène)‐2‐méthylidène‐3,4‐dihydronaphthalène ((Z)‐ and (E)‐8). En concordance avec des calculs quantiques de haut niveau (pseudo‐G3), 12 ne réagit pas avec le SO2 en dehors de sa polymérisation (pas de cycloaddition) alors que les (E)‐1‐fluoro‐1,3‐diènes s'additionnent au SO2 plus rapidement que leurs isomères (Z) en donnant des 6‐fluorosultines. Ces additions du type hétéro‐Diels–Alder suivent la règle (endo) d'Alder. En accord avec les calculs quantiques, le 4‐oxide de cis‐2‐fluoro‐3,4‐oxathiabenzobicyclo[4.4.0]dec‐1‐(6),9‐diène (cis‐9, la sultine résultant de l'addition hetero‐Diels–Alder du SO2 sur (Z)‐8 sous conditions de contrôle cinétique) adopte une conformation sofa avec l'atome d'oxygène cyclique se plaçant dans le plan moyen des quatre atomes de carbone de l'entité sultine, à l'état cristallin à −100 °C. Une conformation sofa similaire est observée à l'état cristallin de l'isomère trans‐9, obtenu par isomérisation de cis‐9 ou par addition selon Diels–Alder du SO2 sur (E)‐8. L'expérience (constantes d'équilibre pour les additions hétéro‐Diels–Alder, les longueurs de liaisons et les angles de liaisons pour les fluorosultines crystallisées cis‐9 et trans‐9) et les calculs quantiques sur les 2‐oxydes de cis‐ et trans‐6‐fluoro‐3,6‐dihydro‐1,2‐oxathiine (cis‐20 and trans‐20) confirment l'existence d'un effet anomère enthalpique (effet de gem‐disubstitution par les groupements sulfinyloxy et fluoro) stabilisant et d'effets anomères conformationels qui sont dominés par une interaction hyperconjugative du type n(O1)→σ*(C−F). Cet effet est le plus marqué dans les conformères sofa où les liaisons σ(O1,S2) et σ(C6,F) sont gauches. Les calculs suggèrent encore que des interactions du type n(O1)→σ*(S2,O2′), π*(S=O) et n(S2)→σ*(O1,C6) interviennent également et affectent la stabilité relative des conformères sofa, bateau et pseudo‐chaise que l'on trouve sur l'hypersurface d'énergie des 6‐fluorosultines cis‐20 et trans‐20.
Unlike other 1‐halodienes, 1‐fluorodienes can undergo hetero‐Diels–Alder addition with SO2. In agreement with quantum calculations, the (E) isomers react more rapidly than the (Z) and tend to undergo the endo (Alder rule) mode of cycloaddition to give fluorosultines, as per the scheme, rather than undergoing cheletropic additions to give fluorosulfolenes. Experiments and high‐level quantum calculations on the sultines confirm the existence of stabilizing enthalpic anomeric effects, which can be interpreted in terms of n(O1)→σ*(C−F) hyperconjugative interaction. This effect is strongest in the sofa conformer, which has the oxygen atom of the ring lying in the average plane of the four carbon atoms.</description><subject>anomeric effects</subject><subject>conformation analysis</subject><subject>cycloaddition</subject><subject>heterocycles</subject><subject>quantum calculations</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><recordid>eNqVkc1uEzEUhUcIREvhFZBXqJXi4J8ZOwkVUpSkSUVJUBtArCzP2FZcJuNgz4jkeXkRPMoPYsGCje17fe53pHuS5BqjLkaIvMUZwZByll2SWCKKs6vegF1jStlgMLwdw9Fs8rGt3tMu6o4W7wi8f5Kcn8aeJueon3LIMto_S16E8IgQ6jNKnydnGPcJJpifJ7-WKw1mutbewbHVZYDDUmkPhkrZ2roKOAMemtI0Hoyt21qlQe0Ahjdl47zLm1pC3KFQWV3pMAAt7cEZCUauMs6vZcsI4JPXRnuvFch3gB2GQ1PWNk6By2MH0g6LqNVOxTfuEOi2sl5ZW8H2Gb3DFZhUj24Xz3oly40tgKzUX2ayBMPKrbWPfxNjdFGHl8kzI8ugXx3ui-TzzWQ5msG7xfR2NLyDRYpSBjEnhiCGU1nEhRNupM7ytChyiikuZEpklmepzJhhsk8kozI1GVGK5wblnCt6kbzZczfe_Wh0qMXahkKXpay0a4LgOEt7qEeicLkXFnELIe5GbLxdS78TGIk2fNGmKNoUxTF80RNMtHELEcMXx_AFFUiMFoKI-4h9ffBv8rVWf6CHtKPg217w05Z691-m__A89SIb7tk21Hp7Ykv_XTBOeSa-zqeCTdGX-ezDXHD6G0Ko2gA</recordid><startdate>20020315</startdate><enddate>20020315</enddate><creator>Roversi, Elena</creator><creator>Scopelliti, Rosario</creator><creator>Solari, Euro</creator><creator>Estoppey, Raphaël</creator><creator>Vogel, Pierre</creator><creator>Braña, Pedro</creator><creator>Menéndez, Bibiana</creator><creator>Sordo, José A.</creator><general>WILEY-VCH Verlag GmbH</general><general>WILEY‐VCH Verlag GmbH</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20020315</creationdate><title>The Hetero-Diels-Alder Addition of Sulfur Dioxide to 1-Fluorobuta-1,3-dienes: The Sofa Conformations Preferred by 6-Fluorosultines (6-Fluoro-3,6-dihydro-1,2-oxathiin-2-oxides) Enjoy Enthalpic and Conformational Anomeric Effects</title><author>Roversi, Elena ; Scopelliti, Rosario ; Solari, Euro ; Estoppey, Raphaël ; Vogel, Pierre ; Braña, Pedro ; Menéndez, Bibiana ; Sordo, José A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4046-172f20614ac00227fae5b4ccb3131ca42a5b54a56f6a92a63a4f52dd7bf0b77d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>anomeric effects</topic><topic>conformation analysis</topic><topic>cycloaddition</topic><topic>heterocycles</topic><topic>quantum calculations</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Roversi, Elena</creatorcontrib><creatorcontrib>Scopelliti, Rosario</creatorcontrib><creatorcontrib>Solari, Euro</creatorcontrib><creatorcontrib>Estoppey, Raphaël</creatorcontrib><creatorcontrib>Vogel, Pierre</creatorcontrib><creatorcontrib>Braña, Pedro</creatorcontrib><creatorcontrib>Menéndez, Bibiana</creatorcontrib><creatorcontrib>Sordo, José A.</creatorcontrib><collection>Istex</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>Roversi, Elena</au><au>Scopelliti, Rosario</au><au>Solari, Euro</au><au>Estoppey, Raphaël</au><au>Vogel, Pierre</au><au>Braña, Pedro</au><au>Menéndez, Bibiana</au><au>Sordo, José A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The Hetero-Diels-Alder Addition of Sulfur Dioxide to 1-Fluorobuta-1,3-dienes: The Sofa Conformations Preferred by 6-Fluorosultines (6-Fluoro-3,6-dihydro-1,2-oxathiin-2-oxides) Enjoy Enthalpic and Conformational Anomeric Effects</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2002-03-15</date><risdate>2002</risdate><volume>8</volume><issue>6</issue><spage>1336</spage><epage>1355</epage><pages>1336-1355</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The reactivity of (E)‐ and (Z)‐1‐fluorobuta‐1,3‐diene ((E)‐ and (Z)‐11), 2‐fluorobutadiene (12), (E)‐ and (Z)‐1‐(fluoromethylidene)‐2‐methylidenecyclohexane ((E)‐ and (Z)‐13) toward SO2 has been explored and compared with that of (Z)‐ and (E)‐1‐(fluoromethylidene)‐2‐methylidene‐3,4‐dihydronaphthalene ((Z)‐8 and (E)‐8). In agreement with quantum calculations, 12 is unreactive toward SO2 (no cycloaddition, only polymerization), whereas (E)‐1‐fluoro‐1,3‐dienes react more rapidly than their (Z)‐isomers to give the corresponding 6‐fluorosultines following the endo (Alder rule) mode of hetero‐Diels–Alder addition. No sulfolene has been observed following the cheletropic mode of addition with the fluorodienes, in contrast to other substituted dienes. In agreement with the calculations, cis‐2‐fluoro‐3,4‐oxathiabenzobicyclo[4.4.0]dec‐1(6),9‐diene‐4‐oxide (cis‐9, the sultine obtained by SO2 addition to (Z)‐8 under conditions of kinetic control) adopts a sofa conformation with the oxygen atom of the ring lying in the average plane of the four carbon atoms of its sultine moiety when it is in the crystalline state at −100 °C. A similar sofa conformation was found for its trans‐isomer, trans‐9, obtained by isomerization of cis‐9 or by hetero‐Diels–Alder addition of SO2 to (E)‐8. Experiments (equilibrium constant for hetero‐Diels–Alder additions, bond lengths, and bond angles in crystalline fluorosultines cis‐9 and trans‐9) and high‐level quantum calculations on cis‐ and trans‐6‐fluoro‐3,6‐dihydro‐1,2‐oxathiin‐2‐oxide (cis‐ and trans‐20) confirm the existence of a stabilizing, enthalpic, anomeric (gem‐disubstitution by sulfinyloxy and fluoro groups) effect, which is interpreted in terms of (lone pair) n(O1)→σ*(C−F) hyperconjugative interactions. This effect is strongest in the sofa conformers with a gauche arrangement of the σ(O1,S2) and σ(C6,F) bonds. The calculations suggest also that n(O1)→σ*(S2,O2′), π*(S=O), and n(S2)→σ*(O1,C6) interactions intervene and affect the relative stability of the conformers (sofa, boat, pseudo‐chair) found for 6‐fluorosultines cis‐ and trans‐20.
La réactivité du SO2 face aux (E)‐ et (Z)‐1‐fluorobuta‐1,3‐diène ((E)‐ et (Z)‐11), 2‐fluorobuta‐1,3‐diène (12), (E) et (Z)‐1‐(fluorométhylidène)‐2‐méthylidènecyclohexane ((E)‐ et (Z)‐13) est étudiée et comparée avec celle du SO2 sur le (Z)‐ et (E)‐1‐(fluorométhylidène)‐2‐méthylidène‐3,4‐dihydronaphthalène ((Z)‐ and (E)‐8). En concordance avec des calculs quantiques de haut niveau (pseudo‐G3), 12 ne réagit pas avec le SO2 en dehors de sa polymérisation (pas de cycloaddition) alors que les (E)‐1‐fluoro‐1,3‐diènes s'additionnent au SO2 plus rapidement que leurs isomères (Z) en donnant des 6‐fluorosultines. Ces additions du type hétéro‐Diels–Alder suivent la règle (endo) d'Alder. En accord avec les calculs quantiques, le 4‐oxide de cis‐2‐fluoro‐3,4‐oxathiabenzobicyclo[4.4.0]dec‐1‐(6),9‐diène (cis‐9, la sultine résultant de l'addition hetero‐Diels–Alder du SO2 sur (Z)‐8 sous conditions de contrôle cinétique) adopte une conformation sofa avec l'atome d'oxygène cyclique se plaçant dans le plan moyen des quatre atomes de carbone de l'entité sultine, à l'état cristallin à −100 °C. Une conformation sofa similaire est observée à l'état cristallin de l'isomère trans‐9, obtenu par isomérisation de cis‐9 ou par addition selon Diels–Alder du SO2 sur (E)‐8. L'expérience (constantes d'équilibre pour les additions hétéro‐Diels–Alder, les longueurs de liaisons et les angles de liaisons pour les fluorosultines crystallisées cis‐9 et trans‐9) et les calculs quantiques sur les 2‐oxydes de cis‐ et trans‐6‐fluoro‐3,6‐dihydro‐1,2‐oxathiine (cis‐20 and trans‐20) confirment l'existence d'un effet anomère enthalpique (effet de gem‐disubstitution par les groupements sulfinyloxy et fluoro) stabilisant et d'effets anomères conformationels qui sont dominés par une interaction hyperconjugative du type n(O1)→σ*(C−F). Cet effet est le plus marqué dans les conformères sofa où les liaisons σ(O1,S2) et σ(C6,F) sont gauches. Les calculs suggèrent encore que des interactions du type n(O1)→σ*(S2,O2′), π*(S=O) et n(S2)→σ*(O1,C6) interviennent également et affectent la stabilité relative des conformères sofa, bateau et pseudo‐chaise que l'on trouve sur l'hypersurface d'énergie des 6‐fluorosultines cis‐20 et trans‐20.
Unlike other 1‐halodienes, 1‐fluorodienes can undergo hetero‐Diels–Alder addition with SO2. In agreement with quantum calculations, the (E) isomers react more rapidly than the (Z) and tend to undergo the endo (Alder rule) mode of cycloaddition to give fluorosultines, as per the scheme, rather than undergoing cheletropic additions to give fluorosulfolenes. Experiments and high‐level quantum calculations on the sultines confirm the existence of stabilizing enthalpic anomeric effects, which can be interpreted in terms of n(O1)→σ*(C−F) hyperconjugative interaction. This effect is strongest in the sofa conformer, which has the oxygen atom of the ring lying in the average plane of the four carbon atoms.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag GmbH</pub><pmid>11921217</pmid><doi>10.1002/1521-3765(20020315)8:6<1336::AID-CHEM1336>3.0.CO;2-R</doi><tpages>20</tpages></addata></record> |
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| subjects | anomeric effects conformation analysis cycloaddition heterocycles quantum calculations |
| title | The Hetero-Diels-Alder Addition of Sulfur Dioxide to 1-Fluorobuta-1,3-dienes: The Sofa Conformations Preferred by 6-Fluorosultines (6-Fluoro-3,6-dihydro-1,2-oxathiin-2-oxides) Enjoy Enthalpic and Conformational Anomeric Effects |
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