Ti(lll)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities.
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| Title: | Ti(lll)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities. |
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| Authors: | Morcillo, Sara P.1, Miguel, Delia1, Resa, Sandra1, Martín-Lasanta, Ana1, Millán, Alba1, Choquesillo-Lazarte, Duane2, García-Ruiz, Juan M.2, Mota, Antonio J.3 mota.avila@gmail.com, Justicia, José1 jjusti@ugr.es, Cuerva, Juan M.1 jmcuerva@ugr.es |
| Source: | Journal of the American Chemical Society. 5/14/2014, Vol. 136 Issue 19, p6943-6951. 9p. |
| Subjects: | Titanium catalyst activity, Ring formation (Chemistry), Stereoselective reactions, Catalysis, Stereochemistry |
| Abstract: | We describe a new strategy to control the number of cyclization steps in bioinspired radical (poly)- cyclizations involving epoxypolyenes containing keto units positioned along the polyene chain. This approach provides an unprecedentedly straightforward access to natural terpenoids with pendant unsaturated side chains. Additionally, in the case of bi- and tricyclizations, decalins with cis stereochemistry have been obtained as a consequence of the presence of the ketone. The preferential formation of cis-fused adducts was rationalized using DFT calculations. This result is completely unprecedented in biomimetic cyclizations and permits the access to natural terpenoids with this stereochemistry, as well as to non-natural analogues. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 96326863 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Ti(lll)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Morcillo%2C+Sara+P%2E%22">Morcillo, Sara P.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Miguel%2C+Delia%22">Miguel, Delia</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Resa%2C+Sandra%22">Resa, Sandra</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Martín-Lasanta%2C+Ana%22">Martín-Lasanta, Ana</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Millán%2C+Alba%22">Millán, Alba</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Choquesillo-Lazarte%2C+Duane%22">Choquesillo-Lazarte, Duane</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22García-Ruiz%2C+Juan+M%2E%22">García-Ruiz, Juan M.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Mota%2C+Antonio+J%2E%22">Mota, Antonio J.</searchLink><relatesTo>3</relatesTo><i> mota.avila@gmail.com</i><br /><searchLink fieldCode="AR" term="%22Justicia%2C+José%22">Justicia, José</searchLink><relatesTo>1</relatesTo><i> jjusti@ugr.es</i><br /><searchLink fieldCode="AR" term="%22Cuerva%2C+Juan+M%2E%22">Cuerva, Juan M.</searchLink><relatesTo>1</relatesTo><i> jmcuerva@ugr.es</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 5/14/2014, Vol. 136 Issue 19, p6943-6951. 9p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Titanium+catalyst+activity%22">Titanium catalyst activity</searchLink><br /><searchLink fieldCode="DE" term="%22Ring+formation+%28Chemistry%29%22">Ring formation (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Stereoselective+reactions%22">Stereoselective reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysis%22">Catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Stereochemistry%22">Stereochemistry</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: We describe a new strategy to control the number of cyclization steps in bioinspired radical (poly)- cyclizations involving epoxypolyenes containing keto units positioned along the polyene chain. This approach provides an unprecedentedly straightforward access to natural terpenoids with pendant unsaturated side chains. Additionally, in the case of bi- and tricyclizations, decalins with cis stereochemistry have been obtained as a consequence of the presence of the ketone. The preferential formation of cis-fused adducts was rationalized using DFT calculations. This result is completely unprecedented in biomimetic cyclizations and permits the access to natural terpenoids with this stereochemistry, as well as to non-natural analogues. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/ja411942h Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 9 StartPage: 6943 Subjects: – SubjectFull: Titanium catalyst activity Type: general – SubjectFull: Ring formation (Chemistry) Type: general – SubjectFull: Stereoselective reactions Type: general – SubjectFull: Catalysis Type: general – SubjectFull: Stereochemistry Type: general Titles: – TitleFull: Ti(lll)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Morcillo, Sara P. – PersonEntity: Name: NameFull: Miguel, Delia – PersonEntity: Name: NameFull: Resa, Sandra – PersonEntity: Name: NameFull: Martín-Lasanta, Ana – PersonEntity: Name: NameFull: Millán, Alba – PersonEntity: Name: NameFull: Choquesillo-Lazarte, Duane – PersonEntity: Name: NameFull: García-Ruiz, Juan M. – PersonEntity: Name: NameFull: Mota, Antonio J. – PersonEntity: Name: NameFull: Justicia, José – PersonEntity: Name: NameFull: Cuerva, Juan M. IsPartOfRelationships: – BibEntity: Dates: – D: 14 M: 05 Text: 5/14/2014 Type: published Y: 2014 Identifiers: – Type: issn-print Value: 00027863 Numbering: – Type: volume Value: 136 – Type: issue Value: 19 Titles: – TitleFull: Journal of the American Chemical Society Type: main |
| ResultId | 1 |
