First general, direct, and regioselective synthesis of substituted methoxybenzoic acids by ortho metalation.
Identifieur interne : 000147 ( PubMed/Corpus ); précédent : 000146; suivant : 000148First general, direct, and regioselective synthesis of substituted methoxybenzoic acids by ortho metalation.
Auteurs : Thi-Huu Nguyen ; Nguyet Trang Thanh Chau ; Anne-Sophie Castanet ; Kim Phi Phung Nguyen ; Jacques MortierSource :
- The Journal of organic chemistry [ 0022-3263 ] ; 2007.
Abstract
New general methodology of value in aromatic chemistry based on ortho-metalation sites in o-, m-, and p-anisic acids (1-3) (Scheme 1) is described. The metalation can be selectively directed to either of the ortho positions by varying the base, metalation temperature, and exposure times. Metalation of o-anisic acid (1) with s-BuLi/TMEDA in THF at -78 degrees C occurs exclusively in the position adjacente to the carboxylate. On the other hand, a reversal of regioselectivity is observed with n-BuLi/t-BuOK. With LTMP at 0 degrees C, the two directors of m-anisic acid (2) function in concert to direct introduction of the metal between them while n-BuLi/t-BuOK removes preferentially the proton located ortho to the methoxy and para to the carboxylate (H-4). s-BuLi/TMEDA reacts with p-anisic acid (3) exclusively in the vicinity of the carboxylate. According to these methodologies, routes to very simple methoxybenzoic acids with a variety of functionalities that are not easily accessible by other means have been developed (Table 1).
DOI: 10.1021/jo070082a
PubMed: 17391047
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The metalation can be selectively directed to either of the ortho positions by varying the base, metalation temperature, and exposure times. Metalation of o-anisic acid (1) with s-BuLi/TMEDA in THF at -78 degrees C occurs exclusively in the position adjacente to the carboxylate. On the other hand, a reversal of regioselectivity is observed with n-BuLi/t-BuOK. With LTMP at 0 degrees C, the two directors of m-anisic acid (2) function in concert to direct introduction of the metal between them while n-BuLi/t-BuOK removes preferentially the proton located ortho to the methoxy and para to the carboxylate (H-4). s-BuLi/TMEDA reacts with p-anisic acid (3) exclusively in the vicinity of the carboxylate. According to these methodologies, routes to very simple methoxybenzoic acids with a variety of functionalities that are not easily accessible by other means have been developed (Table 1).</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="PubMed-not-MEDLINE"><PMID Version="1">17391047</PMID><DateCreated><Year>2007</Year><Month>04</Month><Day>20</Day></DateCreated><DateCompleted><Year>2007</Year><Month>06</Month><Day>29</Day></DateCompleted><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Print">0022-3263</ISSN><JournalIssue CitedMedium="Print"><Volume>72</Volume><Issue>9</Issue><PubDate><Year>2007</Year><Month>Apr</Month><Day>27</Day></PubDate></JournalIssue><Title>The Journal of organic chemistry</Title><ISOAbbreviation>J. Org. Chem.</ISOAbbreviation></Journal><ArticleTitle>First general, direct, and regioselective synthesis of substituted methoxybenzoic acids by ortho metalation.</ArticleTitle><Pagination><MedlinePgn>3419-29</MedlinePgn></Pagination><Abstract><AbstractText>New general methodology of value in aromatic chemistry based on ortho-metalation sites in o-, m-, and p-anisic acids (1-3) (Scheme 1) is described. The metalation can be selectively directed to either of the ortho positions by varying the base, metalation temperature, and exposure times. Metalation of o-anisic acid (1) with s-BuLi/TMEDA in THF at -78 degrees C occurs exclusively in the position adjacente to the carboxylate. On the other hand, a reversal of regioselectivity is observed with n-BuLi/t-BuOK. With LTMP at 0 degrees C, the two directors of m-anisic acid (2) function in concert to direct introduction of the metal between them while n-BuLi/t-BuOK removes preferentially the proton located ortho to the methoxy and para to the carboxylate (H-4). s-BuLi/TMEDA reacts with p-anisic acid (3) exclusively in the vicinity of the carboxylate. According to these methodologies, routes to very simple methoxybenzoic acids with a variety of functionalities that are not easily accessible by other means have been developed (Table 1).</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Nguyen</LastName><ForeName>Thi-Huu</ForeName><Initials>TH</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>Chau</LastName><ForeName>Nguyet Trang Thanh</ForeName><Initials>NT</Initials></Author><Author ValidYN="Y"><LastName>Castanet</LastName><ForeName>Anne-Sophie</ForeName><Initials>AS</Initials></Author><Author ValidYN="Y"><LastName>Nguyen</LastName><ForeName>Kim Phi Phung</ForeName><Initials>KP</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><ArticleDate DateType="Electronic"><Year>2007</Year><Month>03</Month><Day>29</Day></ArticleDate></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>J Org Chem</MedlineTA><NlmUniqueID>2985193R</NlmUniqueID><ISSNLinking>0022-3263</ISSNLinking></MedlineJournalInfo></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="aheadofprint"><Year>2007</Year><Month>3</Month><Day>29</Day></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2007</Year><Month>3</Month><Day>30</Day><Hour>9</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2007</Year><Month>3</Month><Day>30</Day><Hour>9</Hour><Minute>1</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2007</Year><Month>3</Month><Day>30</Day><Hour>9</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1021/jo070082a</ArticleId><ArticleId IdType="pubmed">17391047</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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