Selectivities in reactions of organolithium reagents with unprotected 2-halobenzoic acids.
Identifieur interne : 000190 ( PubMed/Checkpoint ); précédent : 000189; suivant : 000191Selectivities in reactions of organolithium reagents with unprotected 2-halobenzoic acids.
Auteurs : Frédéric Gohier [France] ; Anne-Sophie Castanet ; Jacques MortierSource :
- Organic letters [ 1523-7060 ] ; 2003.
Abstract
[reaction: see text] Exposing 2-fluorobenzoic acid (1a) to 2.2 equiv of LTMP at ca. -78 degrees C leads to deprotonation at the 3-position whereas 2-chloro/bromobenzoic acids (1b,c) are lithiated adjacent to the carboxylate. The resulting dianions 3Li-1a and 6Li-1b,c are trapped as such by chlorotrimethylsilane. In the absence of internal quench, 6Li-1b,c isomerize to the more stable 3Li-1b,c. The latter eliminate lithium halide and set free benzyne-3-carboxylate (2) that reacts regioselectively with LTMP to give 3-tetramethylpiperidinobenzoic acid (3).
DOI: 10.1021/ol034491e
PubMed: 12762686
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The resulting dianions 3Li-1a and 6Li-1b,c are trapped as such by chlorotrimethylsilane. In the absence of internal quench, 6Li-1b,c isomerize to the more stable 3Li-1b,c. The latter eliminate lithium halide and set free benzyne-3-carboxylate (2) that reacts regioselectively with LTMP to give 3-tetramethylpiperidinobenzoic acid (3).</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="PubMed-not-MEDLINE"><PMID Version="1">12762686</PMID><DateCreated><Year>2003</Year><Month>05</Month><Day>23</Day></DateCreated><DateCompleted><Year>2003</Year><Month>09</Month><Day>08</Day></DateCompleted><Article PubModel="Print"><Journal><ISSN IssnType="Print">1523-7060</ISSN><JournalIssue CitedMedium="Print"><Volume>5</Volume><Issue>11</Issue><PubDate><Year>2003</Year><Month>May</Month><Day>29</Day></PubDate></JournalIssue><Title>Organic letters</Title><ISOAbbreviation>Org. Lett.</ISOAbbreviation></Journal><ArticleTitle>Selectivities in reactions of organolithium reagents with unprotected 2-halobenzoic acids.</ArticleTitle><Pagination><MedlinePgn>1919-22</MedlinePgn></Pagination><Abstract><AbstractText>[reaction: see text] Exposing 2-fluorobenzoic acid (1a) to 2.2 equiv of LTMP at ca. -78 degrees C leads to deprotonation at the 3-position whereas 2-chloro/bromobenzoic acids (1b,c) are lithiated adjacent to the carboxylate. The resulting dianions 3Li-1a and 6Li-1b,c are trapped as such by chlorotrimethylsilane. In the absence of internal quench, 6Li-1b,c isomerize to the more stable 3Li-1b,c. The latter eliminate lithium halide and set free benzyne-3-carboxylate (2) that reacts regioselectively with LTMP to give 3-tetramethylpiperidinobenzoic acid (3).</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Gohier</LastName><ForeName>Frédéric</ForeName><Initials>F</Initials><AffiliationInfo><Affiliation>Université du Maine and CNRS, Unité de chimie organique moléculaire et macromoléculaire (UMR 6011), Faculté des sciences, avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Castanet</LastName><ForeName>Anne-Sophie</ForeName><Initials>AS</Initials></Author><Author ValidYN="Y"><LastName>Mortier</LastName><ForeName>Jacques</ForeName><Initials>J</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>Org Lett</MedlineTA><NlmUniqueID>100890393</NlmUniqueID><ISSNLinking>1523-7052</ISSNLinking></MedlineJournalInfo></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="pubmed"><Year>2003</Year><Month>5</Month><Day>24</Day><Hour>5</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2003</Year><Month>5</Month><Day>24</Day><Hour>5</Hour><Minute>1</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2003</Year><Month>5</Month><Day>24</Day><Hour>5</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">12762686</ArticleId><ArticleId IdType="doi">10.1021/ol034491e</ArticleId></ArticleIdList></PubmedData></pubmed><affiliations><list><country><li>France</li></country><region><li>Pays de la Loire</li></region><settlement><li>Le Mans</li></settlement></list><tree><noCountry><name sortKey="Castanet, Anne Sophie" sort="Castanet, Anne Sophie" uniqKey="Castanet A" first="Anne-Sophie" last="Castanet">Anne-Sophie Castanet</name><name sortKey="Mortier, Jacques" sort="Mortier, Jacques" uniqKey="Mortier J" first="Jacques" last="Mortier">Jacques Mortier</name></noCountry><country name="France"><region name="Pays de la Loire"><name sortKey="Gohier, Frederic" sort="Gohier, Frederic" uniqKey="Gohier F" first="Frédéric" last="Gohier">Frédéric Gohier</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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