Synthesis of Alkynyl-substituted Camphor Derivatives and their Use in the Preparation of Paclitaxel-related Compounds.

Hdl Handle:
http://hdl.handle.net/10034/620547
Title:
Synthesis of Alkynyl-substituted Camphor Derivatives and their Use in the Preparation of Paclitaxel-related Compounds.
Authors:
Carvalho, M. F. N. N.; Herrmann, R.; Wagner, G.
Abstract:
Compounds containing two alkyne groups in close vicinity at the rigid skeleton of camphorsulfonamide show unique reactivities when treated with electrophiles or catalytic amounts of platinum(II), the product structures depending not only on the reagents but also on the substituents attached to the triple bonds. Cycloisomerisations with perfect atom economy lead to polycyclic heterocycles that resemble to some extent the AB ring system of paclitaxel. Herein, we present practical synthetic methods for the selective synthesis of precursor dialkynes bearing different substituents (alkyl, aryl) at the triple bonds, based on ketals or an imine as protecting groups. We show for isomeric dialkynes that the reaction cascade induced by Pt(II) includes ring annulation, sulfur reduction and ring enlargement. One isomeric dialkyne additionally allows for the isolation of a pentacyclic compound lacking the ring enlargement step, which we have proposed as a potential intermediate in the catalytic cycle.
Affiliation:
Universidade de Lisboa, University of Augsburg, University of Chester
Citation:
Carvalho, M. F. N. N., Herrmann, R. & Wagner, G. (2017). Synthesis of alkynyl-substituted camphor derivatives and their use in the preparation of paclitaxel-related compounds. BJOC (13), 1230-1238. doi:10.3762/bjoc.13.122
Publisher:
Beilstein
Journal:
Beilstein Journal of Organic Chemistry
Publication Date:
26-Jun-2017
URI:
http://hdl.handle.net/10034/620547
DOI:
10.3762/bjoc.13.122
Type:
Article
Language:
en
Appears in Collections:
Natural Sciences

Full metadata record

DC FieldValue Language
dc.contributor.authorCarvalho, M. F. N. N.en
dc.contributor.authorHerrmann, R.en
dc.contributor.authorWagner, G.en
dc.date.accessioned2017-06-27T10:16:42Z-
dc.date.available2017-06-27T10:16:42Z-
dc.date.issued2017-06-26-
dc.identifier.citationCarvalho, M. F. N. N., Herrmann, R. & Wagner, G. (2017). Synthesis of alkynyl-substituted camphor derivatives and their use in the preparation of paclitaxel-related compounds. BJOC (13), 1230-1238. doi:10.3762/bjoc.13.122en
dc.identifier.doi10.3762/bjoc.13.122-
dc.identifier.urihttp://hdl.handle.net/10034/620547-
dc.description.abstractCompounds containing two alkyne groups in close vicinity at the rigid skeleton of camphorsulfonamide show unique reactivities when treated with electrophiles or catalytic amounts of platinum(II), the product structures depending not only on the reagents but also on the substituents attached to the triple bonds. Cycloisomerisations with perfect atom economy lead to polycyclic heterocycles that resemble to some extent the AB ring system of paclitaxel. Herein, we present practical synthetic methods for the selective synthesis of precursor dialkynes bearing different substituents (alkyl, aryl) at the triple bonds, based on ketals or an imine as protecting groups. We show for isomeric dialkynes that the reaction cascade induced by Pt(II) includes ring annulation, sulfur reduction and ring enlargement. One isomeric dialkyne additionally allows for the isolation of a pentacyclic compound lacking the ring enlargement step, which we have proposed as a potential intermediate in the catalytic cycle.en
dc.language.isoenen
dc.publisherBeilsteinen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectPlatinum Catalysisen
dc.subjectPaclitaxel Analoguesen
dc.subjectCancer treatmenten
dc.titleSynthesis of Alkynyl-substituted Camphor Derivatives and their Use in the Preparation of Paclitaxel-related Compounds.en
dc.typeArticleen
dc.contributor.departmentUniversidade de Lisboa, University of Augsburg, University of Chesteren
dc.identifier.journalBeilstein Journal of Organic Chemistryen
dc.date.accepted2017-05-26-
or.grant.openaccessYesen
rioxxterms.funderFundação para a Ciência e Tecnologia, Portugal. Dr. Ing. Leonhard Lorenz Foundation, Fond der Chemischen Industrie, Germany.en
rioxxterms.identifier.projectfunded through projects located at other Universitiesen
rioxxterms.versionAMen
rioxxterms.licenseref.startdate2017-06-26-
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