Total synthesis of the cytotoxic threo, trans, threo, trans, threo annonaceous acetogenin asimin and its C-10 epimer: unambiguous confirmation of absolute stereochemistry.
Identifieur interne : 003B26 ( Main/Exploration ); précédent : 003B25; suivant : 003B27Total synthesis of the cytotoxic threo, trans, threo, trans, threo annonaceous acetogenin asimin and its C-10 epimer: unambiguous confirmation of absolute stereochemistry.
Auteurs : RBID : pubmed:10479317English descriptors
- KwdEn :
- MESH :
- chemical , chemical synthesis : Furans, Lactones.
- chemical , chemistry : Furans, Lactones.
- chemical : Alcohols.
- Cyclization, Isomerism, Molecular Conformation.
Abstract
A convergent synthesis of asimin (1) and its C-10 epimer 33 is reported. The essential features of this synthesis include (a) the addition of an enantioenriched gamma-OMOM allylic indium reagent to a core C-23 aldehyde precursor to install the C-24-C-34 segment with concomitant introduction of the C-24 and C-23 stereocenters; (b) the addition of an enantioenriched gamma-OMOM allylic indium reagent to a core C-16 aldehyde to install the C-10-C-15 segment with formation of the C-15 and C-16 stereocenters, (c) the addition of a dialkyl zinc reagent, catalyzed by a chiral triflamide-Ti(O-i-Pr)(4) complex, to introduce the C-1-C-9 segment with creation of either the 10(R) or 10(S) stereocenters; and (d) aldol condensation of the foregoing C-1-C-34 segment with OTBS-protected lactic aldehyde to incorporate the C-35-C-37 butenolide segment. Removal of the three MOM protecting groups was achieved with aqueous HCl in THF. The 10(R) diastereomer was found to correspond to natural asimin.
DOI: 10.1021/np990132+
PubMed: 10479317
Links toward previous steps (curation, corpus...)
Le document en format XML
<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Total synthesis of the cytotoxic threo, trans, threo, trans, threo annonaceous acetogenin asimin and its C-10 epimer: unambiguous confirmation of absolute stereochemistry.</title><author><name sortKey="Marshall, J A" uniqKey="Marshall J">J A Marshall</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901, USA. jam5x@virginia.edu</nlm:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901</wicri:regionArea></affiliation></author><author><name sortKey="Jiang, H" uniqKey="Jiang H">H Jiang</name></author></titleStmt><publicationStmt><date when="1999">1999</date><idno type="RBID">pubmed:10479317</idno><idno type="pmid">10479317</idno><idno type="doi">10.1021/np990132+</idno><idno type="wicri:Area/Main/Corpus">003E19</idno><idno type="wicri:Area/Main/Curation">003E19</idno><idno type="wicri:Area/Main/Exploration">003B26</idno></publicationStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Alcohols</term><term>Cyclization</term><term>Furans (chemical synthesis)</term><term>Furans (chemistry)</term><term>Isomerism</term><term>Lactones (chemical synthesis)</term><term>Lactones (chemistry)</term><term>Molecular Conformation</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemical synthesis" xml:lang="en"><term>Furans</term><term>Lactones</term></keywords><keywords scheme="MESH" type="chemical" qualifier="chemistry" xml:lang="en"><term>Furans</term><term>Lactones</term></keywords><keywords scheme="MESH" type="chemical" xml:lang="en"><term>Alcohols</term></keywords><keywords scheme="MESH" xml:lang="en"><term>Cyclization</term><term>Isomerism</term><term>Molecular Conformation</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">A convergent synthesis of asimin (1) and its C-10 epimer 33 is reported. The essential features of this synthesis include (a) the addition of an enantioenriched gamma-OMOM allylic indium reagent to a core C-23 aldehyde precursor to install the C-24-C-34 segment with concomitant introduction of the C-24 and C-23 stereocenters; (b) the addition of an enantioenriched gamma-OMOM allylic indium reagent to a core C-16 aldehyde to install the C-10-C-15 segment with formation of the C-15 and C-16 stereocenters, (c) the addition of a dialkyl zinc reagent, catalyzed by a chiral triflamide-Ti(O-i-Pr)(4) complex, to introduce the C-1-C-9 segment with creation of either the 10(R) or 10(S) stereocenters; and (d) aldol condensation of the foregoing C-1-C-34 segment with OTBS-protected lactic aldehyde to incorporate the C-35-C-37 butenolide segment. Removal of the three MOM protecting groups was achieved with aqueous HCl in THF. The 10(R) diastereomer was found to correspond to natural asimin.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="MEDLINE"><PMID Version="1">10479317</PMID><DateCreated><Year>1999</Year><Month>11</Month><Day>30</Day></DateCreated><DateCompleted><Year>1999</Year><Month>11</Month><Day>30</Day></DateCompleted><DateRevised><Year>2007</Year><Month>11</Month><Day>14</Day></DateRevised><Article PubModel="Print"><Journal><ISSN IssnType="Print">0163-3864</ISSN><JournalIssue CitedMedium="Print"><Volume>62</Volume><Issue>8</Issue><PubDate><Year>1999</Year><Month>Aug</Month></PubDate></JournalIssue><Title>Journal of natural products</Title><ISOAbbreviation>J. Nat. Prod.</ISOAbbreviation></Journal><ArticleTitle>Total synthesis of the cytotoxic threo, trans, threo, trans, threo annonaceous acetogenin asimin and its C-10 epimer: unambiguous confirmation of absolute stereochemistry.</ArticleTitle><Pagination><MedlinePgn>1123-7</MedlinePgn></Pagination><Abstract><AbstractText>A convergent synthesis of asimin (1) and its C-10 epimer 33 is reported. The essential features of this synthesis include (a) the addition of an enantioenriched gamma-OMOM allylic indium reagent to a core C-23 aldehyde precursor to install the C-24-C-34 segment with concomitant introduction of the C-24 and C-23 stereocenters; (b) the addition of an enantioenriched gamma-OMOM allylic indium reagent to a core C-16 aldehyde to install the C-10-C-15 segment with formation of the C-15 and C-16 stereocenters, (c) the addition of a dialkyl zinc reagent, catalyzed by a chiral triflamide-Ti(O-i-Pr)(4) complex, to introduce the C-1-C-9 segment with creation of either the 10(R) or 10(S) stereocenters; and (d) aldol condensation of the foregoing C-1-C-34 segment with OTBS-protected lactic aldehyde to incorporate the C-35-C-37 butenolide segment. Removal of the three MOM protecting groups was achieved with aqueous HCl in THF. The 10(R) diastereomer was found to correspond to natural asimin.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Marshall</LastName><ForeName>J A</ForeName><Initials>JA</Initials><Affiliation>Department of Chemistry, University of Virginia, Charlottesville, Virginia 22901, USA. jam5x@virginia.edu</Affiliation></Author><Author ValidYN="Y"><LastName>Jiang</LastName><ForeName>H</ForeName><Initials>H</Initials></Author></AuthorList><Language>eng</Language><GrantList CompleteYN="Y"><Grant><GrantID>R01 GM56769</GrantID><Acronym>GM</Acronym><Agency>NIGMS NIH HHS</Agency><Country>United States</Country></Grant></GrantList><PublicationTypeList><PublicationType>Journal Article</PublicationType><PublicationType>Research Support, U.S. Gov't, P.H.S.</PublicationType></PublicationTypeList></Article><MedlineJournalInfo><Country>UNITED STATES</Country><MedlineTA>J Nat Prod</MedlineTA><NlmUniqueID>7906882</NlmUniqueID><ISSNLinking>0163-3864</ISSNLinking></MedlineJournalInfo><ChemicalList><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Alcohols</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Furans</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Lactones</NameOfSubstance></Chemical><Chemical><RegistryNumber>156162-01-5</RegistryNumber><NameOfSubstance>asimin</NameOfSubstance></Chemical></ChemicalList><CitationSubset>IM</CitationSubset><MeshHeadingList><MeshHeading><DescriptorName MajorTopicYN="N">Alcohols</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Cyclization</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Furans</DescriptorName><QualifierName MajorTopicYN="Y">chemical synthesis</QualifierName><QualifierName MajorTopicYN="N">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Isomerism</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Lactones</DescriptorName><QualifierName MajorTopicYN="Y">chemical synthesis</QualifierName><QualifierName MajorTopicYN="N">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Molecular Conformation</DescriptorName></MeshHeading></MeshHeadingList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="pubmed"><Year>1999</Year><Month>9</Month><Day>10</Day></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>1999</Year><Month>9</Month><Day>10</Day><Hour>0</Hour><Minute>1</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>1999</Year><Month>9</Month><Day>10</Day><Hour>0</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">10479317</ArticleId><ArticleId IdType="doi">10.1021/np990132+</ArticleId><ArticleId IdType="pii">np990132+</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=IndiumV2/Data/Main/Exploration
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 003B26 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Main/Exploration/biblio.hfd -nk 003B26 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= *** parameter Area/wikiCode missing ***
|area= IndiumV2
|flux= Main
|étape= Exploration
|type= RBID
|clé= pubmed:10479317
|texte= Total synthesis of the cytotoxic threo, trans, threo, trans, threo annonaceous acetogenin asimin and its C-10 epimer: unambiguous confirmation of absolute stereochemistry.
}}
Pour générer des pages wiki
HfdIndexSelect -h $EXPLOR_AREA/Data/Main/Exploration/RBID.i -Sk "pubmed:10479317" \
| HfdSelect -Kh $EXPLOR_AREA/Data/Main/Exploration/biblio.hfd \
| NlmPubMed2Wicri -a IndiumV2
| This area was generated with Dilib version V0.5.76. |  |