Ti(lll)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities.
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 unsa...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 19; pp. 6943 - 6952 |
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| Autores principales: | , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
5/14/2014
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=96326863&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 96326863 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 5/14/2014 vid: 136 iid: 19 pid: 997 pub: American Chemical Society artinfo: ui: 96326863 10.1021/ja411942h ppf: 6943 ppct: 9 formats: tig: atl: Ti(lll)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities. aug: au: Morcillo, Sara P. Miguel, Delia Resa, Sandra Martín-Lasanta, Ana Millán, Alba Choquesillo-Lazarte, Duane García-Ruiz, Juan M. Mota, Antonio J. Justicia, José Cuerva, Juan M. affil: Department of Organic Chemistry,Faculty of Sciences, University of Granada, C. U. Fuentenueva s/n, 18071 Granada, Spain Laboratorio de Estudios Cristalográficos, IACT, CSIC-University of Granada, Avda. de las Palmeras 4, 18100, Armilla (Granada),Spain Department of Inorganic Chemistry, Faculty of Sciences, University of Granada, C. U. Fuentenueva s/n, 18071 Granada, Spain su: Titanium catalyst activity Ring formation (Chemistry) Stereoselective reactions Catalysis Stereochemistry sug: subj: Titanium catalyst activity Ring formation (Chemistry) Stereoselective reactions Catalysis Stereochemistry ab: 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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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