A Facile and Stereocontrolled Synthesis of γ-Substituted γ-Fluoroglutamates by Conjugate Addition: Conflicting Effect between Fluorinated Enaminoester and Hinderered Michael Acceptor
Asymmetric Michael addition of chiral 2-fluoroenaminoesters derived from (S)-1-phenylethylamine to α-substituted methyl acrylate leads to diastereomeric γ-substituted γ-fluoroglutamate precursors. The tertiary center bearing the amino acid function in its natural configuration is generated with a hi...
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| Veröffentlicht in: | Journal of organic chemistry 2010-11, Vol.75 (22), p.7596-7604 |
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| container_title | Journal of organic chemistry |
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| creator | Drège, Emmanuelle Guillaume, Anaïs Boukhedimi, Nadjia Marrot, Jérôme Troufflard, Claire Tran Huu-Dau, Marie-Elise Joseph, Delphine Delarue-Cochin, Sandrine |
| description | Asymmetric Michael addition of chiral 2-fluoroenaminoesters derived from (S)-1-phenylethylamine to α-substituted methyl acrylate leads to diastereomeric γ-substituted γ-fluoroglutamate precursors. The tertiary center bearing the amino acid function in its natural configuration is generated with a high level of stereocontrol in contrast to the quaternary carbon center. Diastereomeric γ-substituted γ-fluoroglutamates were efficiently separated and isolated as thioketal derivatives harboring very good enantioselectivity. The Michael addition diastereoselectivity was studied for the asymmetric conjugate addition of fluorinated chiral β-enaminoester to methyl α-acetamidoacrylate by 19F and 1H NMR experiments as well as ab initio computations. An interfering conjunction between hindrance of the electrophile and a destabilizing effect of the fluorine atom borne by the nucleophile is revealed. |
| doi_str_mv | 10.1021/jo101417c |
| format | Article |
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The tertiary center bearing the amino acid function in its natural configuration is generated with a high level of stereocontrol in contrast to the quaternary carbon center. Diastereomeric γ-substituted γ-fluoroglutamates were efficiently separated and isolated as thioketal derivatives harboring very good enantioselectivity. The Michael addition diastereoselectivity was studied for the asymmetric conjugate addition of fluorinated chiral β-enaminoester to methyl α-acetamidoacrylate by 19F and 1H NMR experiments as well as ab initio computations. An interfering conjunction between hindrance of the electrophile and a destabilizing effect of the fluorine atom borne by the nucleophile is revealed.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo101417c</identifier><identifier>PMID: 21033685</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Alanine - analogs & derivatives ; Alanine - chemistry ; Catalysis ; Chemical Sciences ; Chemistry ; Exact sciences and technology ; Fluorine - chemistry ; Glutamates - chemical synthesis ; Glutamates - chemistry ; Halogenation ; Heterocyclic compounds ; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives ; Magnetic Resonance Spectroscopy ; Molecular Structure ; Organic chemistry ; Preparations and properties ; Stereoisomerism</subject><ispartof>Journal of organic chemistry, 2010-11, Vol.75 (22), p.7596-7604</ispartof><rights>Copyright © 2010 American Chemical Society</rights><rights>2015 INIST-CNRS</rights><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a379t-30ce1284c93ec636256188ff5c82425849e397ada8a4ee0ce4960c408dbdb2653</citedby><cites>FETCH-LOGICAL-a379t-30ce1284c93ec636256188ff5c82425849e397ada8a4ee0ce4960c408dbdb2653</cites><orcidid>0000-0002-5351-4908 ; 0000-0002-7795-4457</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo101417c$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo101417c$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=23531571$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/21033685$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-00551656$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Drège, Emmanuelle</creatorcontrib><creatorcontrib>Guillaume, Anaïs</creatorcontrib><creatorcontrib>Boukhedimi, Nadjia</creatorcontrib><creatorcontrib>Marrot, Jérôme</creatorcontrib><creatorcontrib>Troufflard, Claire</creatorcontrib><creatorcontrib>Tran Huu-Dau, Marie-Elise</creatorcontrib><creatorcontrib>Joseph, Delphine</creatorcontrib><creatorcontrib>Delarue-Cochin, Sandrine</creatorcontrib><title>A Facile and Stereocontrolled Synthesis of γ-Substituted γ-Fluoroglutamates by Conjugate Addition: Conflicting Effect between Fluorinated Enaminoester and Hinderered Michael Acceptor</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Asymmetric Michael addition of chiral 2-fluoroenaminoesters derived from (S)-1-phenylethylamine to α-substituted methyl acrylate leads to diastereomeric γ-substituted γ-fluoroglutamate precursors. The tertiary center bearing the amino acid function in its natural configuration is generated with a high level of stereocontrol in contrast to the quaternary carbon center. Diastereomeric γ-substituted γ-fluoroglutamates were efficiently separated and isolated as thioketal derivatives harboring very good enantioselectivity. The Michael addition diastereoselectivity was studied for the asymmetric conjugate addition of fluorinated chiral β-enaminoester to methyl α-acetamidoacrylate by 19F and 1H NMR experiments as well as ab initio computations. An interfering conjunction between hindrance of the electrophile and a destabilizing effect of the fluorine atom borne by the nucleophile is revealed.</description><subject>Alanine - analogs & derivatives</subject><subject>Alanine - chemistry</subject><subject>Catalysis</subject><subject>Chemical Sciences</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Fluorine - chemistry</subject><subject>Glutamates - chemical synthesis</subject><subject>Glutamates - chemistry</subject><subject>Halogenation</subject><subject>Heterocyclic compounds</subject><subject>Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Molecular Structure</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Stereoisomerism</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkc2O0zAQgC0EYsvCgRdAviDBIeDfNOEWVS1FKuKwcI4cZ9K6cu1iO6A-FxeegmfC2S3tBV-smfn0eTyD0EtK3lHC6Pu9p4QKOteP0IxKRoqyJuIxmhHCWMFZyW_Qsxj3JB8p5VN0wyjhvKzkDP1u8EppYwEr1-O7BAG89i4Fby3kxMmlHUQTsR_wn1_F3djFZNKYci2HKzv64Ld2TOqgEkTcnfDCu_24zRFu-t4k492HKTdYo5NxW7wcBtAJd5B-Ajh8rzBOTcalUwfjPMTcxn0_a-P63FHItc9G7xRY3GgNx-TDc_RkUDbCi_N9i76tll8X62Lz5eOnRbMpFJ_XqeBEA2WV0DUHXfKSyZJW1TBIXTHBZCVq4PVc9apSAiDDoi6JFqTqu75jpeS36O2Dd6dsewzmoMKp9cq062bTTrlpprSU5Q-a2TcP7DH472P-RnswUYO1yoEfY0tFXVNGBWNXrQ4-xgDDxU1JOy21vSw1s6_O2rE7QH8h_20xA6_PgIpa2SEop028clxyKuf0yikds38MLk_uPw_-Bc2SuSE</recordid><startdate>20101119</startdate><enddate>20101119</enddate><creator>Drège, Emmanuelle</creator><creator>Guillaume, Anaïs</creator><creator>Boukhedimi, Nadjia</creator><creator>Marrot, Jérôme</creator><creator>Troufflard, Claire</creator><creator>Tran Huu-Dau, Marie-Elise</creator><creator>Joseph, Delphine</creator><creator>Delarue-Cochin, Sandrine</creator><general>American Chemical Society</general><scope>IQODW</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><scope>1XC</scope><orcidid>https://orcid.org/0000-0002-5351-4908</orcidid><orcidid>https://orcid.org/0000-0002-7795-4457</orcidid></search><sort><creationdate>20101119</creationdate><title>A Facile and Stereocontrolled Synthesis of γ-Substituted γ-Fluoroglutamates by Conjugate Addition: Conflicting Effect between Fluorinated Enaminoester and Hinderered Michael Acceptor</title><author>Drège, Emmanuelle ; Guillaume, Anaïs ; Boukhedimi, Nadjia ; Marrot, Jérôme ; Troufflard, Claire ; Tran Huu-Dau, Marie-Elise ; Joseph, Delphine ; Delarue-Cochin, Sandrine</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a379t-30ce1284c93ec636256188ff5c82425849e397ada8a4ee0ce4960c408dbdb2653</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Alanine - analogs & derivatives</topic><topic>Alanine - chemistry</topic><topic>Catalysis</topic><topic>Chemical Sciences</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Fluorine - chemistry</topic><topic>Glutamates - chemical synthesis</topic><topic>Glutamates - chemistry</topic><topic>Halogenation</topic><topic>Heterocyclic compounds</topic><topic>Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Molecular Structure</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Drège, Emmanuelle</creatorcontrib><creatorcontrib>Guillaume, Anaïs</creatorcontrib><creatorcontrib>Boukhedimi, Nadjia</creatorcontrib><creatorcontrib>Marrot, Jérôme</creatorcontrib><creatorcontrib>Troufflard, Claire</creatorcontrib><creatorcontrib>Tran Huu-Dau, Marie-Elise</creatorcontrib><creatorcontrib>Joseph, Delphine</creatorcontrib><creatorcontrib>Delarue-Cochin, Sandrine</creatorcontrib><collection>Pascal-Francis</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><collection>Hyper Article en Ligne (HAL)</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Drège, Emmanuelle</au><au>Guillaume, Anaïs</au><au>Boukhedimi, Nadjia</au><au>Marrot, Jérôme</au><au>Troufflard, Claire</au><au>Tran Huu-Dau, Marie-Elise</au><au>Joseph, Delphine</au><au>Delarue-Cochin, Sandrine</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Facile and Stereocontrolled Synthesis of γ-Substituted γ-Fluoroglutamates by Conjugate Addition: Conflicting Effect between Fluorinated Enaminoester and Hinderered Michael Acceptor</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2010-11-19</date><risdate>2010</risdate><volume>75</volume><issue>22</issue><spage>7596</spage><epage>7604</epage><pages>7596-7604</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Asymmetric Michael addition of chiral 2-fluoroenaminoesters derived from (S)-1-phenylethylamine to α-substituted methyl acrylate leads to diastereomeric γ-substituted γ-fluoroglutamate precursors. The tertiary center bearing the amino acid function in its natural configuration is generated with a high level of stereocontrol in contrast to the quaternary carbon center. Diastereomeric γ-substituted γ-fluoroglutamates were efficiently separated and isolated as thioketal derivatives harboring very good enantioselectivity. The Michael addition diastereoselectivity was studied for the asymmetric conjugate addition of fluorinated chiral β-enaminoester to methyl α-acetamidoacrylate by 19F and 1H NMR experiments as well as ab initio computations. 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| ispartof | Journal of organic chemistry, 2010-11, Vol.75 (22), p.7596-7604 |
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| subjects | Alanine - analogs & derivatives Alanine - chemistry Catalysis Chemical Sciences Chemistry Exact sciences and technology Fluorine - chemistry Glutamates - chemical synthesis Glutamates - chemistry Halogenation Heterocyclic compounds Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives Magnetic Resonance Spectroscopy Molecular Structure Organic chemistry Preparations and properties Stereoisomerism |
| title | A Facile and Stereocontrolled Synthesis of γ-Substituted γ-Fluoroglutamates by Conjugate Addition: Conflicting Effect between Fluorinated Enaminoester and Hinderered Michael Acceptor |
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