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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">A Short Route to the Ester (±) HomoSarkomycin <italic>via</italic> Johnson-Claisen Rearrangement</title><author><name sortKey="Saied, M" sort="Saied, M" uniqKey="Saied M" first="M" last="Saied">M. Saied</name><affiliation><nlm:aff id="aff1">Département de Chimie, Faculté des Sciences de Tunis Laboratoire de Synthèse Organique et Hétérocyclique, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country>;</nlm:aff></affiliation></author><author><name sortKey="Gatri, Rafik" sort="Gatri, Rafik" uniqKey="Gatri R" first="Rafik" last="Gatri">Rafik Gatri</name><affiliation><nlm:aff id="aff1">Département de Chimie, Faculté des Sciences de Tunis Laboratoire de Synthèse Organique et Hétérocyclique, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country>;</nlm:aff></affiliation><affiliation><nlm:aff id="aff2">Chemistry Department, College of Science and Arts at Ar Rass, Qassim University, Burayadah<addr-line><postal-code>51477</postal-code>,<country>Saudi Arabia</country></addr-line>;</nlm:aff></affiliation></author><author><name sortKey="Al Ayed, Abdullah Sulaiman" sort="Al Ayed, Abdullah Sulaiman" uniqKey="Al Ayed A" first="Abdullah Sulaiman" last="Al-Ayed">Abdullah Sulaiman Al-Ayed</name><affiliation><nlm:aff id="aff2">Chemistry Department, College of Science and Arts at Ar Rass, Qassim University, Burayadah<addr-line><postal-code>51477</postal-code>,<country>Saudi Arabia</country></addr-line>;</nlm:aff></affiliation></author><author><name sortKey="Arfaoui, Youssef" sort="Arfaoui, Youssef" uniqKey="Arfaoui Y" first="Youssef" last="Arfaoui">Youssef Arfaoui</name><affiliation><nlm:aff id="aff3">Unité Physico Chimie des Matériaux Condensés -UR11ES19, Faculté des Sciences de Tunis, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country></nlm:aff></affiliation></author><author><name sortKey="El Gaied, Mohamed Moncef" sort="El Gaied, Mohamed Moncef" uniqKey="El Gaied M" first="Mohamed Moncef" last="El Gaied">Mohamed Moncef El Gaied</name><affiliation><nlm:aff id="aff2">Chemistry Department, College of Science and Arts at Ar Rass, Qassim University, Burayadah<addr-line><postal-code>51477</postal-code>,<country>Saudi Arabia</country></addr-line>;</nlm:aff></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">PMC</idno><idno type="pmid">29399007</idno><idno type="pmc">5759048</idno><idno type="url">http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5759048</idno><idno type="RBID">PMC:5759048</idno><idno type="doi">10.2174/1570178614666161230123513</idno><date when="2017">2017</date><idno type="wicri:Area/Pmc/Corpus">000217</idno><idno type="wicri:explorRef" wicri:stream="Pmc" wicri:step="Corpus" wicri:corpus="PMC">000217</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en" level="a" type="main">A Short Route to the Ester (±) HomoSarkomycin <italic>via</italic> Johnson-Claisen Rearrangement</title><author><name sortKey="Saied, M" sort="Saied, M" uniqKey="Saied M" first="M" last="Saied">M. Saied</name><affiliation><nlm:aff id="aff1">Département de Chimie, Faculté des Sciences de Tunis Laboratoire de Synthèse Organique et Hétérocyclique, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country>;</nlm:aff></affiliation></author><author><name sortKey="Gatri, Rafik" sort="Gatri, Rafik" uniqKey="Gatri R" first="Rafik" last="Gatri">Rafik Gatri</name><affiliation><nlm:aff id="aff1">Département de Chimie, Faculté des Sciences de Tunis Laboratoire de Synthèse Organique et Hétérocyclique, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country>;</nlm:aff></affiliation><affiliation><nlm:aff id="aff2">Chemistry Department, College of Science and Arts at Ar Rass, Qassim University, Burayadah<addr-line><postal-code>51477</postal-code>,<country>Saudi Arabia</country></addr-line>;</nlm:aff></affiliation></author><author><name sortKey="Al Ayed, Abdullah Sulaiman" sort="Al Ayed, Abdullah Sulaiman" uniqKey="Al Ayed A" first="Abdullah Sulaiman" last="Al-Ayed">Abdullah Sulaiman Al-Ayed</name><affiliation><nlm:aff id="aff2">Chemistry Department, College of Science and Arts at Ar Rass, Qassim University, Burayadah<addr-line><postal-code>51477</postal-code>,<country>Saudi Arabia</country></addr-line>;</nlm:aff></affiliation></author><author><name sortKey="Arfaoui, Youssef" sort="Arfaoui, Youssef" uniqKey="Arfaoui Y" first="Youssef" last="Arfaoui">Youssef Arfaoui</name><affiliation><nlm:aff id="aff3">Unité Physico Chimie des Matériaux Condensés -UR11ES19, Faculté des Sciences de Tunis, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country></nlm:aff></affiliation></author><author><name sortKey="El Gaied, Mohamed Moncef" sort="El Gaied, Mohamed Moncef" uniqKey="El Gaied M" first="Mohamed Moncef" last="El Gaied">Mohamed Moncef El Gaied</name><affiliation><nlm:aff id="aff2">Chemistry Department, College of Science and Arts at Ar Rass, Qassim University, Burayadah<addr-line><postal-code>51477</postal-code>,<country>Saudi Arabia</country></addr-line>;</nlm:aff></affiliation></author></analytic><series><title level="j">Letters in Organic Chemistry</title><idno type="ISSN">1570-1786</idno><idno type="eISSN">1875-6255</idno><imprint><date when="2017">2017</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en"><sec><title>Background:</title><p>α-Methylene cycloalkanones are considered of interest because of their biological activity. Herein, in this paper the synthesis of (±) HomoSarkomycine Esters was described and characterized.</p></sec><sec><title>Methods:</title><p>Using Bylis-Hillman adducts, triethlorthoacetate and propanoic acid, (±) HomoSarkomycine Esters could be synthesized by smoothly Johnson-Claisen rearrangement.</p></sec><sec><title>Results:</title><p>A small library of target compounds was prepared under optimized reaction conditions in moderate yields. The reaction mechanism and the DFT study have been investigated.</p></sec><sec><title>Conclusion:</title><p>This methodology provides ready access to 2-hydroxymethyl-2-cyclopentenone 1a which can be served as the raw materials of the synthesis of (±) HomoSarkomycine Ester.</p></sec></div></front><back><div1 type="bibliography"><listBibl><biblStruct><analytic><author><name sortKey="Marx, J N" uniqKey="Marx J">J.N. Marx</name></author><author><name sortKey="Minaskanian, G" uniqKey="Minaskanian G">G. 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<front><journal-meta><journal-id journal-id-type="nlm-ta">Lett Org Chem</journal-id><journal-id journal-id-type="iso-abbrev">Lett Org Chem</journal-id><journal-id journal-id-type="publisher-id">LOC</journal-id><journal-title-group><journal-title>Letters in Organic Chemistry</journal-title></journal-title-group><issn pub-type="ppub">1570-1786</issn><issn pub-type="epub">1875-6255</issn><publisher><publisher-name>Bentham Science Publishers</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="pmid">29399007</article-id><article-id pub-id-type="pmc">5759048</article-id><article-id pub-id-type="publisher-id">LOC-14-181</article-id><article-id pub-id-type="doi">10.2174/1570178614666161230123513</article-id><article-categories><subj-group subj-group-type="heading"><subject>Article</subject></subj-group></article-categories><title-group><article-title>A Short Route to the Ester (±) HomoSarkomycin <italic>via</italic> Johnson-Claisen Rearrangement</article-title></title-group><contrib-group><contrib contrib-type="author"><name><surname>Saied</surname><given-names>M</given-names></name><xref ref-type="aff" rid="aff1">1</xref></contrib><contrib contrib-type="author"><name><surname>Gatri</surname><given-names>Rafik</given-names></name><xref ref-type="aff" rid="aff1">1</xref><xref ref-type="aff" rid="aff2">2</xref><xref ref-type="corresp" rid="cor1">*</xref></contrib><contrib contrib-type="author"><name><surname>Al-Ayed</surname><given-names>Abdullah Sulaiman</given-names></name><xref ref-type="aff" rid="aff2">2</xref></contrib><contrib contrib-type="author"><name><surname>Arfaoui</surname><given-names>Youssef</given-names></name><xref ref-type="aff" rid="aff3">3</xref></contrib><contrib contrib-type="author"><name><surname>El Gaied</surname><given-names>Mohamed Moncef</given-names></name><xref ref-type="aff" rid="aff2">2</xref></contrib><aff id="aff1"><label>1</label>Département de Chimie, Faculté des Sciences de Tunis Laboratoire de Synthèse Organique et Hétérocyclique, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country>;</aff><aff id="aff2"><label>2</label>Chemistry Department, College of Science and Arts at Ar Rass, Qassim University, Burayadah<addr-line><postal-code>51477</postal-code>,<country>Saudi Arabia</country></addr-line>;</aff><aff id="aff3"><label>3</label>Unité Physico Chimie des Matériaux Condensés -UR11ES19, Faculté des Sciences de Tunis, Campus Universitaire,<institution>Université Tunis El Manar 2</institution>,<addr-line><postal-code>2092</postal-code><city>Tunis</city></addr-line>,<country>Tunisia</country></aff></contrib-group><author-notes><corresp id="cor1"><label>*</label>Address correspondence to this author at the Department of Chemistry, College of Sciences and Arts at Ar Rass, Qassim University, P.O. Box: 51477, Buraydah, Saudi Arabia; Tel: 00966563680500; E-mail: <email xlink:href="rafik.gatri@gmail.com">rafik.gatri@gmail.com</email></corresp></author-notes><pub-date pub-type="epub"><month>3</month><year>2017</year></pub-date><pub-date pub-type="ppub"><month>3</month><year>2017</year></pub-date><volume>14</volume><issue>3</issue><fpage>181</fpage><lpage>185</lpage><history><date date-type="received"><day>07</day><month>10</month><year>2016</year></date><date date-type="rev-recd"><day>29</day><month>11</month><year>2016</year></date><date date-type="accepted"><day>20</day><month>12</month><year>2016</year></date></history><permissions><copyright-statement>© 2017 Bentham Science Publishers</copyright-statement><copyright-year>2017</copyright-year><license license-type="open-access" xlink:href="https://creativecommons.org/licenses/by-nc/4.0/legalcode"><license-p> This is an open access article licensed under the terms of the Creative Commons Attribution-Non-Commercial 4.0 International Public License (CC BY-NC 4.0) <uri xlink:href="https://creativecommons.org/licenses/by-nc/4.0/legalcode">(https://creativecommons.org/licenses/by-nc/4.0/legalcode</uri>), which permits unrestricted, non-commercial use, distribution and reproduction in any medium, provided the work is properly cited.</license-p></license></permissions><abstract><sec><title>Background:</title><p>α-Methylene cycloalkanones are considered of interest because of their biological activity. Herein, in this paper the synthesis of (±) HomoSarkomycine Esters was described and characterized.</p></sec><sec><title>Methods:</title><p>Using Bylis-Hillman adducts, triethlorthoacetate and propanoic acid, (±) HomoSarkomycine Esters could be synthesized by smoothly Johnson-Claisen rearrangement.</p></sec><sec><title>Results:</title><p>A small library of target compounds was prepared under optimized reaction conditions in moderate yields. The reaction mechanism and the DFT study have been investigated.</p></sec><sec><title>Conclusion:</title><p>This methodology provides ready access to 2-hydroxymethyl-2-cyclopentenone 1a which can be served as the raw materials of the synthesis of (±) HomoSarkomycine Ester.</p></sec></abstract><kwd-group kwd-group-type="author"><title>Keywords: </title><kwd>Baylis-Hillman reaction</kwd><kwd>homosarkomycine</kwd><kwd>2-hydroxymethylcyclopentenone</kwd><kwd>Johnson-Claisen rearrangement</kwd></kwd-group></article-meta></front><body><sec sec-type="intro"><label>1.</label><title>INTRODUCTION</title><p>α-Methylene cycloalkanones [<xref rid="r1" ref-type="bibr">1</xref>-<xref rid="r12" ref-type="bibr">12</xref>] (Fig. <bold><xref ref-type="fig" rid="F1">1</xref></bold>) are considered as versatile intermediates to natural products [<xref rid="r13" ref-type="bibr">13</xref>-<xref rid="r15" ref-type="bibr">15</xref>] and are of current interest because of their anti-tumor activity [<xref rid="r16" ref-type="bibr">16</xref>, <xref rid="r17" ref-type="bibr">17</xref>]. Some examples of active compounds are presented below [<xref rid="r18" ref-type="bibr">18</xref>-<xref rid="r20" ref-type="bibr">20</xref>]. Smith III, A.B. <italic>et al.</italic> prepared (±)HomoSarkomycin Ester 2a by the Johnson-Claisen rearrangement of the ketal of 1a, after hydrolysis of the ester and ketal functionalities [<xref rid="r16" ref-type="bibr">16</xref>].</p><p>In continuation of our interest in the synthesis of biological compounds [<xref rid="r21" ref-type="bibr">21</xref>-<xref rid="r23" ref-type="bibr">23</xref>], we established an efficient synthesis of the (±) HomoSarkomycin Ester 2a <italic>via</italic> a Johnson-Claisen rearrangement using the Baylis-Hillman adduct 1a (Scheme <bold><xref ref-type="fig" rid="S1">1</xref></bold>), that was prepared (in our laboratory) [<xref rid="r24" ref-type="bibr">24</xref>] in one step from 2-cyclopentenone in high yield and in relatively high scale.</p></sec><sec><label>2.</label><title>RESULTS AND DISCUSSIONS</title><p>The Baylis-Hillman reaction produces highly functionalized adducts such as <bold>1a</bold> [<xref rid="r24" ref-type="bibr">24</xref>] which may serve as the startingmaterials for the synthesis of useful targets. We envisaged that the Johnson-Claisen rearrangement [<xref rid="r25" ref-type="bibr">25</xref>] would be a powerful and practical route to the (±) HomoSarkomycine Ester <bold>2a</bold> (Scheme <bold><xref ref-type="fig" rid="S1">1</xref></bold>).</p><p>The reaction between 2-hydroxymethyl-2-cyclopentenone (<bold>1a</bold>) [<xref rid="r24" ref-type="bibr">24</xref>] and triethyl orthoacetate in the presence of propanoic acid at 150°C leads to (±) HomoSarkomycine Ester (<bold>2a</bold>) <italic>via</italic> a [<xref rid="r3" ref-type="bibr">3</xref>, <xref rid="r3" ref-type="bibr">3</xref>] sigma-tropic rearrangement (Scheme <bold><xref ref-type="fig" rid="S1">1</xref></bold>, Table <bold>1</bold>).</p><p>In a second step, we studied if this Johnson-Claisen rearrangement can be generalized in order to access to α-alkylidene-β-methylethoxycarbonyl cyclopentanones <bold>2b-d</bold> [<xref rid="r24" ref-type="bibr">24</xref>] (Scheme <bold><xref ref-type="fig" rid="S2">2</xref></bold>, Table <bold>1</bold>). The corresponding α-alkylidene cyclopentanone adducts were obtained in moderate yield in all the cases.</p><p>It should be noted that the reaction with <bold>1e</bold> results in the esterification product <bold>2e</bold> instead of the rearrangement (Scheme <bold><xref ref-type="fig" rid="S3">3</xref></bold>).</p><p>A plausible mechanism for the formation of compounds <bold>2a-d</bold> and <bold>2e</bold> is depicted in Scheme <bold><xref ref-type="fig" rid="S4">4</xref></bold>.</p><p>These mechanisms are supported by the following calculations.</p><sec><title>Computational Details</title><p>The geometries of the CH<sub>3</sub>-C(OC<sub>2</sub>H<sub>5</sub>)<sub>3</sub>, CH<sub>3</sub>CH<sub>2</sub>-COOH, 2-(1-hydroxyethyl)cyclopentenone <bold>1b</bold> and 2-(phenyl-hydroxymethyl)cyclopentenone <bold>1e</bold> are optimized by Density Functional Theory calculations applying the functional B3LYP and the 6-31G (d) basis set and using the GAUSSIAN 09 program [<xref rid="r26" ref-type="bibr">26</xref>-<xref rid="r28" ref-type="bibr">28</xref>]. To characterize the reactivity, we used Fukui function, defined as the differential change in electron density due to an infinitesimal change in the number of electrons. The condensed Fukui functions of an atom, say k, in a molecule with N electrons are defined for nucleophilic and electrophilic attack, respectively as:</p><p><inline-formula><mml:math id="m1"><mml:msubsup><mml:mrow><mml:mi>f</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msubsup><mml:mo>=</mml:mo><mml:mi mathvariant="normal"> </mml:mi><mml:msub><mml:mrow><mml:mi>q</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi><mml:mi mathvariant="normal"> </mml:mi></mml:mrow></mml:msub><mml:mfenced separators="|"><mml:mrow><mml:mi>N</mml:mi><mml:mo>+</mml:mo><mml:mn>1</mml:mn></mml:mrow></mml:mfenced><mml:mo>-</mml:mo><mml:mi mathvariant="normal"> </mml:mi><mml:msub><mml:mrow><mml:mi>q</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi><mml:mi mathvariant="normal"> </mml:mi></mml:mrow></mml:msub><mml:mfenced separators="|"><mml:mrow><mml:mi>N</mml:mi></mml:mrow></mml:mfenced></mml:math></inline-formula></p><p><inline-formula><mml:math id="m2"><mml:msubsup><mml:mrow><mml:mi>f</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi></mml:mrow><mml:mrow><mml:mo>-</mml:mo></mml:mrow></mml:msubsup><mml:mo>=</mml:mo><mml:mi mathvariant="normal"> </mml:mi><mml:msub><mml:mrow><mml:mi>q</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi><mml:mi mathvariant="normal"> </mml:mi></mml:mrow></mml:msub><mml:mfenced separators="|"><mml:mrow><mml:mi>N</mml:mi></mml:mrow></mml:mfenced><mml:mo>-</mml:mo><mml:mi mathvariant="normal"> </mml:mi><mml:msub><mml:mrow><mml:mi>q</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi><mml:mi mathvariant="normal"> </mml:mi></mml:mrow></mml:msub><mml:mfenced separators="|"><mml:mrow><mml:mi>N</mml:mi><mml:mo>-</mml:mo><mml:mn>1</mml:mn></mml:mrow></mml:mfenced></mml:math></inline-formula></p><p>Where <italic>q<sub>k</sub></italic> is the electronic population of atom k in a molecule. The corresponding local softness parameters can be defined as [<xref rid="r29" ref-type="bibr">29</xref>-<xref rid="r31" ref-type="bibr">31</xref>]:</p><p><inline-formula><mml:math id="m3"><mml:msubsup><mml:mrow><mml:mi>S</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msubsup><mml:mo>=</mml:mo><mml:mi>S</mml:mi><mml:mi mathvariant="normal"> </mml:mi><mml:msubsup><mml:mrow><mml:mi>f</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msubsup><mml:mi mathvariant="normal"> </mml:mi><mml:mo>;</mml:mo><mml:mi mathvariant="normal"> </mml:mi><mml:msubsup><mml:mrow><mml:mi>S</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi></mml:mrow><mml:mrow><mml:mo>-</mml:mo></mml:mrow></mml:msubsup><mml:mo>=</mml:mo><mml:mi mathvariant="normal"> </mml:mi><mml:mi>S</mml:mi><mml:mi mathvariant="normal"> </mml:mi><mml:msubsup><mml:mrow><mml:mi>f</mml:mi></mml:mrow><mml:mrow><mml:mi>k</mml:mi></mml:mrow><mml:mrow><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:math></inline-formula></p><p>The global softness is defined as <inline-formula><mml:math id="m4"><mml:mi>S</mml:mi><mml:mo>=</mml:mo><mml:mi> </mml:mi><mml:mfrac><mml:mrow><mml:mn>1</mml:mn></mml:mrow><mml:mrow><mml:mn>2</mml:mn><mml:mi mathvariant="normal">η</mml:mi><mml:mi> </mml:mi></mml:mrow></mml:mfrac></mml:math></inline-formula>.</p><p>The hardness is given by η = <inline-formula><mml:math id="m5"><mml:mfrac><mml:mrow><mml:msub><mml:mrow><mml:mi>E</mml:mi></mml:mrow><mml:mrow><mml:mi>L</mml:mi><mml:mi>U</mml:mi><mml:mi>M</mml:mi><mml:mi>O</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:mi mathvariant="normal"> </mml:mi><mml:msub><mml:mrow><mml:mi>E</mml:mi></mml:mrow><mml:mrow><mml:mi>H</mml:mi><mml:mi>O</mml:mi><mml:mi>M</mml:mi><mml:mi>O</mml:mi></mml:mrow></mml:msub><mml:mi mathvariant="normal"> </mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:mfrac></mml:math></inline-formula>.</p><p>Results of local reactivity properties of the selected molecules are summarized in Table <bold>2</bold> and <xref ref-type="fig" rid="F2">Fig. (<bold><xref ref-type="fig" rid="F2">2</xref></bold>)</xref>.</p><p>In this study, we have presented the reactivity parameters, the local softness and of the corresponding propanoic acid, orthoester and the two Baylis-Hillman adducts (<bold>1b</bold> and <bold>1e</bold>) and the most reactive sites for nucleophilic and electrophilic attack were derived. If we match the values of the C<sub>3</sub> and H<sub>4</sub> atoms of the orthoester and propanoic acid, respectively with values of the oxygen O<sub>1</sub> and O<sub>2</sub> in the OH group of the Bayliss-Hillman adducts 1b and 1e, respectively, one finds clearly that the of the O<sub>1</sub> atom match better with the values of the of C<sub>3</sub> atom, whereas the of the O<sub>2</sub> atom match better with the H<sub>4</sub> atom (Fig. <bold><xref ref-type="fig" rid="F3">3</xref></bold>). Thus the local HSAB principle also predicts the reaction in accordance with the experimentally proved evidence.</p></sec></sec><sec><label>3.</label><title>EXPERIMENTAL</title><p>Proton (<sup>1</sup>H) and carbon (<sup>13</sup>C) nuclear magnetic resonance (NMR) spectra were recorded on a Bruker AC-300 MHz spectrometer as a solution in deuterochloroform. Infrared (IR) spectra were recorded on a Perkin–Elmer Spectrum (FT_IR specter Pargon 1000 PC). The products are dosed on an automatic analyzer type SCA-CHN with detector of thermal conductivity-meter: catharometer (INRAP, Tunisia). The plates used for thin-layer chromatography (TLC) were E. Merck silica gel 60F254 (0.25 mm thickness) precoated on aluminum plates, and they were visualized under both long (365 nm) and short (254 nm) UV light. All compounds were purified by column chromatography (Silica gel 60, 70-230 mesh ASTM). Mass Spectra (MS) were carried out on a Hewlett-Packard 5890 (70 ev) by the staff of Medicine Faculty of Monastir, Tunisia, under electronic impact (EI) using NH<sub>3</sub> as the carrier gas.</p><sec><label>3.1.</label><title>Representative Procedure for the Synthesis of 2a-e</title><p>A 25 mL round bottomed flask was charged with 2-hydroxymethyl-2-cyclopentenone <bold>1a</bold> (3 mmol, 336 mg), triethylorthoacetate (3.6 mmol, 583 mg) and propionic acid (3 mmol, 222 mg). The resulting mixture was stirred at reflux for 4 hours. When the reaction was completed, the mixture was basified by 5 mL of saturated solution of NaHCO<sub>3</sub> and extracted with 40 mL of ethyl acetate. After the usual work, the crude product was purified by column chromatography on silica gel using Diethyl ether/Petroleum ether (1:9) as eluent, gave pure <bold>2a</bold> in 70% yield.</p><sec><label>3.1.1.</label><title>3-Ethoxycarbonylmethyl-2-methylenecyclopentan-1-one (2a)</title><p>IR (CHCl<sub>3</sub>) cm<sup>-1</sup>: 1727 (C=O, ester), 1708 (C=O, ketone). <sup>1</sup>H NMR (300 MHz, CDCl<sub>3</sub>): 6.05-5.28 (AA’, <italic>J</italic> = 2.9 Hz, 2H), 4.19 (q, <italic>J</italic> = 6.9 Hz, 2H,), 3.20 (m, 1H), 2.73-2.66 (d, 1H), 2.47-2.17 (m, 4H), 1.58 (m, 1H), 1.30 (t, <italic>J</italic> = 6.9 Hz, 3H). <sup>13</sup>C NMR (75 MHz, CDCl<sub>3</sub>): 206.1, 171.8, 147.6, 117.1, 60.6, 38.9; 37.5, 36.9, 26.5, 14.2. MS (<italic>m/z</italic>): 41(39), 53 (88), 67 (71), 79 (64), 98 (73), 108 (100), 125 (46), 137 (57), 154 (86), 182 (M<sup>+</sup>; 65). Elemental Analysis for C<sub>10</sub>H<sub>14</sub>O<sub>3</sub> calcld: C, 65.91 H, 7.74 found: C, 65.98; H, 7.86.</p></sec><sec><label>3.1.2.</label><title>3-Ethoxycarbonylmethyl-2-ethylidenecyclopentan-1-one (2b)</title><p>IR (CHCl<sub>3</sub>) cm<sup>-1</sup>: 1715 (C=O, ester), 1698 (C=O, ketone). <sup>1</sup>H NMR (300 MHz, CDCl<sub>3</sub>): 6.66 et 6.03 (q, <italic>J</italic> = 2.9 Hz, 1H), 4.17 (q, <italic>J</italic> = 6.9 Hz, 2H), 3.48 (m, 1H), 2.38-2.05 (m, 6H), 1.88 (d, <italic>J</italic> = 2.9 Hz, 3H), 1.27 (t, <italic>J</italic> = 6.9 Hz, 3H). <sup>13</sup>C NMR (75 MHz, CDCl<sub>3</sub>): 206.0, 171.5, 147.1, 125.2, 60.4, 38.6, 37.3, 35.9, 26.4, 24.3, 14.1. MS (<italic>m/z</italic>): 41 (27), 67 (21), 79 (43), 109 (100), 123 (39), 151 (19) 196 (M<sup>+</sup>; 65). Elemental Analysis for C<sub>11</sub>H<sub>16</sub>O<sub>3</sub> calcld: C, 67.32; H, 8.22 found: C, 67.40; H, 8.33.</p></sec><sec><label>3.1.3.</label><title>3-Ethoxycarbonylmethyl-2-butylidenecyclopentan-1-one (2c)</title><p>IR (CHCl<sub>3</sub>) cm<sup>-1</sup>: 1717 (C=O, ester), 1695 (C=O, ketone). <sup>1</sup>H NMR (300 MHz, CDCl<sub>3</sub>): 6.64 and 5.56 (t, J = 2.9 Hz, 1H), 4.22 (q, <italic>J</italic> = 6.9 Hz, 2H), 2.58 (m, 4H), 2.44-2.34 (m, 4H), 2.05-1.71 (m, 4H), 1.25 (m, 2H), 1.15 (t, <italic>J</italic> = 6.9 Hz, 3H), 0.91 (m, 3H). <sup>13</sup>C NMR (75 MHz, CDCl<sub>3</sub>): 207.3, 173.6, 158.3, 145.6, 69.2, 35.3, 35.1, 29.7, 27.7, 26.5, 18.5, 13.7, 9.2. MS (m/z): 41 (13), 55 (15), 67 (18), 79 (21), 95 (21), 107 (11), 121 (11), 137 (100), 224 (M<sup>+</sup>; 29). Elemental Analysis for C<sub>13</sub>H<sub>20</sub>O<sub>3</sub> calcd: C, 69.61; H, 8.99, found: C, 69.55; H, 9.12.</p></sec><sec><label>3.1.4.</label><title>3-Ethoxycarbonylmethyl-2-(2-methylpropylidene) cyclopentan-1-one (2d)</title><p>IR (CHCl<sub>3</sub>) cm<sup>-1</sup>: 1722 (C=O, ester), 1703 (C=O, ketone). <sup>1</sup>H NMR (300 MHz, CDCl<sub>3</sub>): 6.41 (d, J = 2.9 Hz, 1H), 4.17 (q, J = 6.9 Hz, 2H), 3.74 (m, 1H), 2.44-1.85 (m, 7H), 1.25 (t, J = 6.9 Hz, 3H), 1.04 (m, 6H). <sup>13</sup>C NMR (75 MHz, CDCl<sub>3</sub>): 207.0, 171.8, 144.2, 137.4, 60.7, 39.4, 35.8, 34.8, 29.7, 28.7 25.2, 22.1, 14.2. MS (m/z): 41 (13), 55 (14), 67 (17), 79 (23) 95 (18), 109 (16), 121 (10), 137 (100), 179 (8), 224 (M<sup>+</sup>; 30). Elemental Analysis for C<sub>13</sub>H<sub>20</sub>O<sub>3</sub> calcd: C, 69.61; H, 8.99, found: C, 69.54; H, 9.12.</p></sec><sec><label>3.1.5.</label><title>2-(1-Phenyl-propanoyloxyméthyl)cyclopent-2-en-1-one (2e)</title><p>IR (CHCl<sub>3</sub>) cm<sup>-1</sup>: 1743 (C=O, ester), 1701 (C=O, ketone). <sup>1</sup>H NMR (300 MHz, CDCl<sub>3</sub>): 7.48 (m, 1H), 7.37-7.18 (m, 5H), 6.54 (s, 1H), 2.58 (m, 2H), 2.45-2.29 (m, 4H), 1.17 (t, <italic>J</italic> = 7.3 Hz, 3H). <sup>13</sup>C NMR (75 MHz, CDCl<sub>3</sub>): 206.5, 171.9, 159.2, 145.4, 138.2, 128.4, 128.3, 127.2, 70.2, 34.9, 27.6, 26.6, 9.0. MS (m/z): 57(98), 77(28), 109(55), 128 (97), 141(16), 141(16), 159(14), 171(20), 187(100), 244 (M<sup>+</sup>; 2). Elemental Analysis for C<sub>15</sub>H<sub>16</sub>O<sub>3</sub> calcd: C, 73.75; H, 6.60, found: C, 73.78; H, 6.71.</p></sec></sec></sec><sec sec-type="conclusions"><title>CONCLUSION</title><p>In the present study, we have reported the preparation of the (±) HomoSarkomycine Ester <bold>2a</bold> in one step from 2-hydroxymethl-2-cyclopentenone <bold>1a</bold>. We have succeeded to generalize this process with Baylis-Hillman adducts <bold>1b-e</bold>. Local reactivity descriptors are shown to be very powerful in predicting the reactivity of Baylis-Hillman adducts <bold>1a-e</bold>, propanoic acid and triethylorthoester.</p></sec></body><back><ack><title>ACKNOWLEDGEMENTS</title><p>The authors would like to extend their sincere appreciation to the Deanship of Scientific Research at Qassim University for funding this research group No (3208).</p></ack><sec sec-type="supplementary-material"><title>SUPPLEMENTARY MATERIAL</title><supplementary-material content-type="local-data" id="SD1"><p>Supplementary material is available on the publisher’s web site along with the published article.</p><media mimetype="application" mime-subtype="pdf" xlink:href="LOC-14-181_SD1.pdf" orientation="portrait" id="d35e988" position="anchor"></media></supplementary-material></sec><sec><title>CONFLICT OF INTEREST</title><p>The author(s) confirm that this article content has no conflict of interest.</p></sec><ref-list><title>REFERENCES</title><ref id="r1"><label>1</label><element-citation publication-type="journal"><person-group person-group-type="author"><name><surname>Marx</surname><given-names>J.N.</given-names></name><name><surname>Minaskanian</surname><given-names>G.</given-names></name></person-group><article-title>2-Carbemethoxycyclopentenone as a Synthon. 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Simul.</source><year>2008</year><volume>34</volume><fpage>931</fpage><lpage>936</lpage></element-citation></ref></ref-list></back><floats-group><fig id="F1" fig-type="figure" orientation="portrait" position="float"><label>Fig. (1)</label><caption><p>Structures of α-Methylene cycloalkanones.</p></caption><graphic xlink:href="LOC-14-181_F1"></graphic></fig><fig id="F2" fig-type="figure" orientation="portrait" position="float"><label>Fig. (2)</label><caption><p>The 4 atoms O<sub>1</sub>, O<sub>2</sub>, C<sub>3</sub> and H<sub>4</sub>.</p></caption><graphic xlink:href="LOC-14-181_F2"></graphic></fig><fig id="F3" fig-type="figure" orientation="portrait" position="float"><label>Fig. (3)</label><caption><p>Local softness for the 4 atoms O<sub>1</sub>, O<sub>2</sub>, C<sub>3</sub> and H<sub>4</sub>.</p></caption><graphic xlink:href="LOC-14-181_F3"></graphic></fig><fig id="S1" fig-type="figure" orientation="portrait" position="float"><label>Scheme (1)</label><caption><p>Synthesis of (±) HomoSarkomycin Ester <bold>2a</bold>.</p></caption><graphic xlink:href="LOC-14-181_S1"></graphic></fig><fig id="S2" fig-type="figure" orientation="portrait" position="float"><label>Scheme (2)</label><caption><p>Synthesis of α-alkylidene-β-methylethoxycarbonyl cyclopentanones <bold>2b-d</bold>.</p></caption><graphic xlink:href="LOC-14-181_S2"></graphic></fig><fig id="S3" fig-type="figure" orientation="portrait" position="float"><label>Scheme (3)</label><caption><p>Synthesis of 2-(1-Phenyl-propanoyloxyméthyl)cyclopent-2-en-1-one <bold>2e</bold>.</p></caption><graphic xlink:href="LOC-14-181_S3"></graphic></fig><fig id="S4" fig-type="figure" orientation="portrait" position="float"><label>Scheme (4)</label><caption><p>A plausible mechanism for the formation of compounds <bold>2a-d</bold> and <bold>2e</bold>.</p></caption><graphic xlink:href="LOC-14-181_S4"></graphic></fig><table-wrap id="T1" orientation="portrait" position="float"><label>Table 1</label><caption><p>Synthesis of 2a-d from 1a-d with Johnson-Claisen rearrangement.</p></caption><table frame="border" rules="all" width="100%"><thead><tr><th valign="top" align="center" scope="col" rowspan="1" colspan="1"><bold>2</bold></th><th valign="top" align="center" scope="col" rowspan="1" colspan="1"><bold>a</bold></th><th valign="top" align="center" scope="col" rowspan="1" colspan="1"><bold>b</bold></th><th valign="top" align="center" scope="col" rowspan="1" colspan="1"><bold>c</bold></th><th valign="top" align="center" scope="col" rowspan="1" colspan="1"><bold>d</bold></th></tr></thead><tbody><tr><td valign="top" align="center" scope="row" rowspan="1" colspan="1">R</td><td valign="top" align="center" rowspan="1" colspan="1">H</td><td valign="top" align="center" rowspan="1" colspan="1">Me</td><td valign="top" align="center" rowspan="1" colspan="1">n-Pr</td><td valign="top" align="center" rowspan="1" colspan="1">i-Pr</td></tr><tr><td valign="top" align="center" scope="row" rowspan="1" colspan="1">Time</td><td valign="top" align="center" rowspan="1" colspan="1">4 h</td><td valign="top" align="center" rowspan="1" colspan="1">4 h</td><td valign="top" align="center" rowspan="1" colspan="1">5h 30 mn</td><td valign="top" align="center" rowspan="1" colspan="1">6h</td></tr><tr><td valign="top" align="center" scope="row" rowspan="1" colspan="1"><italic>Z/E</italic><bold><italic>*</italic></bold></td><td valign="top" align="center" rowspan="1" colspan="1">-</td><td valign="top" align="center" rowspan="1" colspan="1">20/80</td><td valign="top" align="center" rowspan="1" colspan="1">30/70</td><td valign="top" align="center" rowspan="1" colspan="1">10/90</td></tr><tr><td valign="top" align="center" scope="row" rowspan="1" colspan="1">Yield (%)</td><td valign="top" align="center" rowspan="1" colspan="1">70</td><td valign="top" align="center" rowspan="1" colspan="1">60</td><td valign="top" align="center" rowspan="1" colspan="1">58</td><td valign="top" align="center" rowspan="1" colspan="1">64</td></tr></tbody></table><table-wrap-foot><p>* The proportion is calculated from the <sup>1</sup>H NMR.</p></table-wrap-foot></table-wrap><table-wrap id="T2" orientation="portrait" position="float"><label>Table 2</label><caption><p>Calculated local reactivity properties of the selected molecules using BLYP/6-31g(d) method for NBO derived charges.</p></caption><table frame="border" rules="all" width="100%"><thead><tr><th valign="middle" align="center" scope="col" rowspan="1" colspan="1"><bold>Entry</bold></th><th valign="middle" align="center" scope="col" rowspan="1" colspan="1"><bold>O<sub>1</sub></bold></th><th valign="middle" align="center" scope="col" rowspan="1" colspan="1"><bold>O<sub>2</sub></bold></th><th valign="middle" align="center" scope="col" rowspan="1" colspan="1"><bold>C<sub>3</sub></bold></th><th valign="middle" align="center" scope="col" rowspan="1" colspan="1"><bold>H<sub>4</sub></bold></th></tr></thead><tbody><tr><td valign="middle" align="left" scope="row" rowspan="1" colspan="1"></td><td valign="middle" align="center" rowspan="1" colspan="1">0.177</td><td valign="middle" align="center" rowspan="1" colspan="1">0.046</td><td valign="middle" align="left" rowspan="1" colspan="1"></td><td valign="middle" align="left" rowspan="1" colspan="1"></td></tr><tr><td valign="middle" align="left" scope="row" rowspan="1" colspan="1"></td><td valign="middle" align="left" rowspan="1" colspan="1"></td><td valign="middle" align="left" rowspan="1" colspan="1"></td><td valign="middle" align="center" rowspan="1" colspan="1">0.423</td><td valign="middle" align="center" rowspan="1" colspan="1">0.116</td></tr><tr><td valign="middle" align="center" scope="row" rowspan="1" colspan="1"><bold><italic>E<sub>LUMO</sub></italic> - <italic>E<sub>HOMO</sub></italic></bold></td><td valign="middle" align="center" rowspan="1" colspan="1">0.19458</td><td valign="middle" align="center" rowspan="1" colspan="1">0.17922</td><td valign="middle" align="center" rowspan="1" colspan="1">0.28787</td><td valign="middle" align="center" rowspan="1" colspan="1">0.27589</td></tr><tr><td valign="middle" align="center" scope="row" rowspan="1" colspan="1">η</td><td valign="middle" align="center" rowspan="1" colspan="1">0.09729</td><td valign="middle" align="center" rowspan="1" colspan="1">0.08961</td><td valign="middle" align="center" rowspan="1" colspan="1">0.14393</td><td valign="middle" align="center" rowspan="1" colspan="1">0.13794</td></tr><tr><td valign="middle" align="center" scope="row" rowspan="1" colspan="1">S</td><td valign="middle" align="center" rowspan="1" colspan="1">5.1390</td><td valign="middle" align="center" rowspan="1" colspan="1">5.5797</td><td valign="middle" align="center" rowspan="1" colspan="1">3.47380</td><td valign="middle" align="center" rowspan="1" colspan="1">3.6250</td></tr><tr><td valign="middle" align="left" scope="row" rowspan="1" colspan="1"></td><td valign="middle" align="center" rowspan="1" colspan="1">0.9096</td><td valign="middle" align="center" rowspan="1" colspan="1">0.2567</td><td valign="middle" align="left" rowspan="1" colspan="1"></td><td valign="middle" align="left" rowspan="1" colspan="1"></td></tr><tr><td valign="middle" align="left" scope="row" rowspan="1" colspan="1"></td><td valign="middle" align="left" rowspan="1" colspan="1"></td><td valign="middle" align="left" rowspan="1" colspan="1"></td><td valign="middle" align="center" rowspan="1" colspan="1">1.4660</td><td valign="middle" align="center" rowspan="1" colspan="1">0.4205</td></tr></tbody></table></table-wrap></floats-group></pmc></record>Pour manipuler ce document sous Unix (Dilib)
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