Synthetic studies towards garsubellin A: synthesis of model systems and potential mimics by regioselective lithiation of bicyclo[3.3.1]nonane-2,4,9-trione derivatives from catechinic acid
Identifieur interne : 000647 ( Istex/Curation ); précédent : 000646; suivant : 000648Synthetic studies towards garsubellin A: synthesis of model systems and potential mimics by regioselective lithiation of bicyclo[3.3.1]nonane-2,4,9-trione derivatives from catechinic acid
Auteurs : Nadia M. Ahmad [Royaume-Uni] ; Vincent Rodeschini [Royaume-Uni] ; Nigel S. Simpkins [Royaume-Uni] ; Simon E. Ward [Royaume-Uni] ; Claire Wilson [Royaume-Uni]Source :
- Organic & Biomolecular Chemistry [ 1477-0520 ] ; 2007.
Descripteurs français
- Wicri :
- topic : Pétrole.
English descriptors
- KwdEn :
- Allyl, Aqueous nacl, Aroch, Aromatic moiety, Biomol, Bridged, Bridged ketone, Bridgehead, Bridgehead position, Bridgehead substitution, Bromide, Carboxylic acid, Catechinic, Catechinic acid, Catechol, Cdcl3, Chcl3, Chcl3 mmax, Chem, Column chromatography, Deep solution, Derivative, Electrophiles, Garsubellin, Hrms, Ketal, Ketone, Lett, Lithiation, Ltmp, Mgso4, Mmax, Mmol, Nacl, Natural products, Organic extracts, Organic layers, Oxidative, Oxidative degradation, Petroleum, Prenyl, Prenyl bromide, Quenched, Reaction mixture, Regioselective lithiation, Royal society, Substituents, Substitution, Tetrahedron lett, Title compound, Total synthesis, Vacuo, Various electrophiles.
- Teeft :
- Allyl, Aqueous nacl, Aroch, Aromatic moiety, Biomol, Bridged, Bridged ketone, Bridgehead, Bridgehead position, Bridgehead substitution, Bromide, Carboxylic acid, Catechinic, Catechinic acid, Catechol, Cdcl3, Chcl3, Chcl3 mmax, Chem, Column chromatography, Deep solution, Derivative, Electrophiles, Garsubellin, Hrms, Ketal, Ketone, Lett, Lithiation, Ltmp, Mgso4, Mmax, Mmol, Nacl, Natural products, Organic extracts, Organic layers, Oxidative, Oxidative degradation, Petroleum, Prenyl, Prenyl bromide, Quenched, Reaction mixture, Regioselective lithiation, Royal society, Substituents, Substitution, Tetrahedron lett, Title compound, Total synthesis, Vacuo, Various electrophiles.
Abstract
Bridgehead lithiations have successfully been carried out on substrates derived from catechinic acid, which possess the core bicyclo[3.3.1]nonane-1,3,5-trione structure present in garsubellin A. Using an external quench method, various electrophiles have been incorporated at the C-5 bridgehead position in a one-step process that appears to be sensitive to the substitution pattern on the bicyclic system. Regioselective lithiation at the C-3 sp2 centre was achieved by changing the base used from LDA to LTMP. Following the introduction of a prenyl substituent by bridgehead substitution, annulation of a THF ring, analogous to that in garsubellin A, was possible via an epoxidation–ring opening sequence. Oxidative modification of the catechol substituent of the catechinic acid core was possible to give systems with muconic acid, ortho-quinone or furan 2-carboxylic acid side chains.
Url:
DOI: 10.1039/b704311b
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<term>Aqueous nacl</term>
<term>Aroch</term>
<term>Aromatic moiety</term>
<term>Biomol</term>
<term>Bridged</term>
<term>Bridged ketone</term>
<term>Bridgehead</term>
<term>Bridgehead position</term>
<term>Bridgehead substitution</term>
<term>Bromide</term>
<term>Carboxylic acid</term>
<term>Catechinic</term>
<term>Catechinic acid</term>
<term>Catechol</term>
<term>Cdcl3</term>
<term>Chcl3</term>
<term>Chcl3 mmax</term>
<term>Chem</term>
<term>Column chromatography</term>
<term>Deep solution</term>
<term>Derivative</term>
<term>Electrophiles</term>
<term>Garsubellin</term>
<term>Hrms</term>
<term>Ketal</term>
<term>Ketone</term>
<term>Lett</term>
<term>Lithiation</term>
<term>Ltmp</term>
<term>Mgso4</term>
<term>Mmax</term>
<term>Mmol</term>
<term>Nacl</term>
<term>Natural products</term>
<term>Organic extracts</term>
<term>Organic layers</term>
<term>Oxidative</term>
<term>Oxidative degradation</term>
<term>Petroleum</term>
<term>Prenyl</term>
<term>Prenyl bromide</term>
<term>Quenched</term>
<term>Reaction mixture</term>
<term>Regioselective lithiation</term>
<term>Royal society</term>
<term>Substituents</term>
<term>Substitution</term>
<term>Tetrahedron lett</term>
<term>Title compound</term>
<term>Total synthesis</term>
<term>Vacuo</term>
<term>Various electrophiles</term>
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<term>Aroch</term>
<term>Aromatic moiety</term>
<term>Biomol</term>
<term>Bridged</term>
<term>Bridged ketone</term>
<term>Bridgehead</term>
<term>Bridgehead position</term>
<term>Bridgehead substitution</term>
<term>Bromide</term>
<term>Carboxylic acid</term>
<term>Catechinic</term>
<term>Catechinic acid</term>
<term>Catechol</term>
<term>Cdcl3</term>
<term>Chcl3</term>
<term>Chcl3 mmax</term>
<term>Chem</term>
<term>Column chromatography</term>
<term>Deep solution</term>
<term>Derivative</term>
<term>Electrophiles</term>
<term>Garsubellin</term>
<term>Hrms</term>
<term>Ketal</term>
<term>Ketone</term>
<term>Lett</term>
<term>Lithiation</term>
<term>Ltmp</term>
<term>Mgso4</term>
<term>Mmax</term>
<term>Mmol</term>
<term>Nacl</term>
<term>Natural products</term>
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<term>Organic layers</term>
<term>Oxidative</term>
<term>Oxidative degradation</term>
<term>Petroleum</term>
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<term>Reaction mixture</term>
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<term>Substituents</term>
<term>Substitution</term>
<term>Tetrahedron lett</term>
<term>Title compound</term>
<term>Total synthesis</term>
<term>Vacuo</term>
<term>Various electrophiles</term>
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<front><div type="abstract">Bridgehead lithiations have successfully been carried out on substrates derived from catechinic acid, which possess the core bicyclo[3.3.1]nonane-1,3,5-trione structure present in garsubellin A. Using an external quench method, various electrophiles have been incorporated at the C-5 bridgehead position in a one-step process that appears to be sensitive to the substitution pattern on the bicyclic system. Regioselective lithiation at the C-3 sp2 centre was achieved by changing the base used from LDA to LTMP. Following the introduction of a prenyl substituent by bridgehead substitution, annulation of a THF ring, analogous to that in garsubellin A, was possible via an epoxidation–ring opening sequence. Oxidative modification of the catechol substituent of the catechinic acid core was possible to give systems with muconic acid, ortho-quinone or furan 2-carboxylic acid side chains.</div>
</front>
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