An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone
Autor(a) principal: | |
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Data de Publicação: | 2001 |
Outros Autores: | |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Journal of the Brazilian Chemical Society (Online) |
Texto Completo: | http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000300007 |
Resumo: | We disclose herein a synthetic approach for the preparation of an unusual carbon skeleton, which was found in nor-sesquiterpenes isolated from marine corals. The main structural feature of this skeleton is the presence of two contiguous quaternary centers, one of them bears a spiro gamma-butyrolactone moiety. One of the quaternary centers was prepared with moderate stereoselectivity by the conjugate addition of lithium dimethylcuprate to 2-methylcyclohexenone, followed by the trapping of the intermediate enolate with allyl bromide to furnish trans-2-allyl-2,3-dimethylcyclohexan-2-one, as a major diastereoisomer. The preparation of the quaternary centers bearing the spiro gamma-butyrolactone moiety was secured by the addition of a suitably functionalized organolithium reagent on trans-2-allyl-2,3-dimetylcyclohexan-2-one, followed by separation of the isomers and two oxidation steps. This strategy has permitted us to report the racemic total synthesis of a non-natural nor-sesquiterpene derivative, in 6 steps and 16% overall yield, from 2-methylcyclohexenone. |
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An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactonenor-sesquiterpenenapalilactonemarine natural productsdehalo-napalilactonepathylactoneWe disclose herein a synthetic approach for the preparation of an unusual carbon skeleton, which was found in nor-sesquiterpenes isolated from marine corals. The main structural feature of this skeleton is the presence of two contiguous quaternary centers, one of them bears a spiro gamma-butyrolactone moiety. One of the quaternary centers was prepared with moderate stereoselectivity by the conjugate addition of lithium dimethylcuprate to 2-methylcyclohexenone, followed by the trapping of the intermediate enolate with allyl bromide to furnish trans-2-allyl-2,3-dimethylcyclohexan-2-one, as a major diastereoisomer. The preparation of the quaternary centers bearing the spiro gamma-butyrolactone moiety was secured by the addition of a suitably functionalized organolithium reagent on trans-2-allyl-2,3-dimetylcyclohexan-2-one, followed by separation of the isomers and two oxidation steps. This strategy has permitted us to report the racemic total synthesis of a non-natural nor-sesquiterpene derivative, in 6 steps and 16% overall yield, from 2-methylcyclohexenone.Sociedade Brasileira de Química2001-06-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000300007Journal of the Brazilian Chemical Society v.12 n.3 2001reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50532001000300007info:eu-repo/semantics/openAccessDiaz,GasparCoelho,Fernandoeng2001-10-03T00:00:00Zoai:scielo:S0103-50532001000300007Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2001-10-03T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone |
title |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone |
spellingShingle |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone Diaz,Gaspar nor-sesquiterpene napalilactone marine natural products dehalo-napalilactone pathylactone |
title_short |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone |
title_full |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone |
title_fullStr |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone |
title_full_unstemmed |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone |
title_sort |
An approach to the construction of the carbon skeleton of marine nor-sesquiterpenes. Total synthesis of (±)-dehalo-napalilactone |
author |
Diaz,Gaspar |
author_facet |
Diaz,Gaspar Coelho,Fernando |
author_role |
author |
author2 |
Coelho,Fernando |
author2_role |
author |
dc.contributor.author.fl_str_mv |
Diaz,Gaspar Coelho,Fernando |
dc.subject.por.fl_str_mv |
nor-sesquiterpene napalilactone marine natural products dehalo-napalilactone pathylactone |
topic |
nor-sesquiterpene napalilactone marine natural products dehalo-napalilactone pathylactone |
description |
We disclose herein a synthetic approach for the preparation of an unusual carbon skeleton, which was found in nor-sesquiterpenes isolated from marine corals. The main structural feature of this skeleton is the presence of two contiguous quaternary centers, one of them bears a spiro gamma-butyrolactone moiety. One of the quaternary centers was prepared with moderate stereoselectivity by the conjugate addition of lithium dimethylcuprate to 2-methylcyclohexenone, followed by the trapping of the intermediate enolate with allyl bromide to furnish trans-2-allyl-2,3-dimethylcyclohexan-2-one, as a major diastereoisomer. The preparation of the quaternary centers bearing the spiro gamma-butyrolactone moiety was secured by the addition of a suitably functionalized organolithium reagent on trans-2-allyl-2,3-dimetylcyclohexan-2-one, followed by separation of the isomers and two oxidation steps. This strategy has permitted us to report the racemic total synthesis of a non-natural nor-sesquiterpene derivative, in 6 steps and 16% overall yield, from 2-methylcyclohexenone. |
publishDate |
2001 |
dc.date.none.fl_str_mv |
2001-06-01 |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000300007 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532001000300007 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.1590/S0103-50532001000300007 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
text/html |
dc.publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
dc.source.none.fl_str_mv |
Journal of the Brazilian Chemical Society v.12 n.3 2001 reponame:Journal of the Brazilian Chemical Society (Online) instname:Sociedade Brasileira de Química (SBQ) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
reponame_str |
Journal of the Brazilian Chemical Society (Online) |
collection |
Journal of the Brazilian Chemical Society (Online) |
repository.name.fl_str_mv |
Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
_version_ |
1750318164248363008 |