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Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones

[Image: see text] The stereospecific ring-opening of O-heterocycles to provide acyclic alcohols and carboxylic acids with controlled formation of a new C–C bond is reported. These reactions provide new methods for synthesis of acyclic polyketide analogs with complex stereochemical arrays. Stereosele...

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Autores principales: Tollefson, Emily J., Dawson, David D., Osborne, Charlotte A., Jarvo, Elizabeth R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4210078/
https://www.ncbi.nlm.nih.gov/pubmed/25308512
http://dx.doi.org/10.1021/ja5076426
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author Tollefson, Emily J.
Dawson, David D.
Osborne, Charlotte A.
Jarvo, Elizabeth R.
author_facet Tollefson, Emily J.
Dawson, David D.
Osborne, Charlotte A.
Jarvo, Elizabeth R.
author_sort Tollefson, Emily J.
collection PubMed
description [Image: see text] The stereospecific ring-opening of O-heterocycles to provide acyclic alcohols and carboxylic acids with controlled formation of a new C–C bond is reported. These reactions provide new methods for synthesis of acyclic polyketide analogs with complex stereochemical arrays. Stereoselective synthesis of the cyclic template is utilized to control relative configuration; subsequent stereospecific nickel-catalyzed ring-opening affords the acyclic product. Aryl-substituted tetrahydrofurans and tetrahydropyrans undergo nickel-catalyzed Kumada-type coupling with a range of Grignard reagents to furnish acyclic alcohols with high diastereoselectivity. Enantioenriched lactones undergo Negishi-type cross-coupling with dimethylzinc to afford enantioenriched carboxylic acids. Application in a two-step enantioselective synthesis of an anti-dyslipidemia agent is demonstrated.
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spelling pubmed-42100782015-10-13 Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones Tollefson, Emily J. Dawson, David D. Osborne, Charlotte A. Jarvo, Elizabeth R. J Am Chem Soc [Image: see text] The stereospecific ring-opening of O-heterocycles to provide acyclic alcohols and carboxylic acids with controlled formation of a new C–C bond is reported. These reactions provide new methods for synthesis of acyclic polyketide analogs with complex stereochemical arrays. Stereoselective synthesis of the cyclic template is utilized to control relative configuration; subsequent stereospecific nickel-catalyzed ring-opening affords the acyclic product. Aryl-substituted tetrahydrofurans and tetrahydropyrans undergo nickel-catalyzed Kumada-type coupling with a range of Grignard reagents to furnish acyclic alcohols with high diastereoselectivity. Enantioenriched lactones undergo Negishi-type cross-coupling with dimethylzinc to afford enantioenriched carboxylic acids. Application in a two-step enantioselective synthesis of an anti-dyslipidemia agent is demonstrated. American Chemical Society 2014-10-13 2014-10-22 /pmc/articles/PMC4210078/ /pubmed/25308512 http://dx.doi.org/10.1021/ja5076426 Text en Copyright © 2014 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html)
spellingShingle Tollefson, Emily J.
Dawson, David D.
Osborne, Charlotte A.
Jarvo, Elizabeth R.
Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones
title Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones
title_full Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones
title_fullStr Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones
title_full_unstemmed Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones
title_short Stereospecific Cross-Coupling Reactions of Aryl-Substituted Tetrahydrofurans, Tetrahydropyrans, and Lactones
title_sort stereospecific cross-coupling reactions of aryl-substituted tetrahydrofurans, tetrahydropyrans, and lactones
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4210078/
https://www.ncbi.nlm.nih.gov/pubmed/25308512
http://dx.doi.org/10.1021/ja5076426
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