Weakening C-O Bonds: Ti(III), a New Reagent for Alcohol Deoxygenation and Carbonyl Coupling Olefination.
Investigations detailed herein, including density functional theory (DFT) calculations, demonstrate that the formation of either alkoxy- or hydroxy-Ti(lll) complexes considerably decreases the energy of activation for C-O bond homolysis. As a consequence of this observation, we described two new syn...
| Published in: | Journal of the American Chemical Society Vol. 132; no. 1; pp. 254 - 260 |
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| Main Authors: | , , , , , , , |
| Format: | Article |
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American Chemical Society
1/13/2010
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=48230217&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 48230217 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: 1/13/2010 vid: 132 iid: 1 pid: 997 pub: American Chemical Society artinfo: ui: 48230217 10.1021/ja906083c ppf: 254 ppct: 6 formats: tig: atl: Weakening C-O Bonds: Ti(III), a New Reagent for Alcohol Deoxygenation and Carbonyl Coupling Olefination. aug: au: Diéguez, Horacio A. López, Armando Domingo, Victoriano Arteaga, Jesús F. Dobado, José A. Herrador, M. Mar QuíIez del Moral, José F. Barrero, Alejandro F. affil: Department of Organic Chemistry, Institute of Biotechnology, University of Granada, Avda. Fuentenueva, 18071 Granada, Spain Department of Chemical Engineering, Physical Chemistry and Organic Chemistry, Faculty of Experimental Sciences, University of Huelva, Campus el Carmen, 21071 Huelva, Spain su: Titanium Metal complexes Carbon Oxygen Alcohols (Chemical class) Carbonyl compounds Density functionals Organic chemistry sug: subj: Titanium Metal complexes Carbon Oxygen Alcohols (Chemical class) Carbonyl compounds Density functionals Organic chemistry ab: Investigations detailed herein, including density functional theory (DFT) calculations, demonstrate that the formation of either alkoxy- or hydroxy-Ti(lll) complexes considerably decreases the energy of activation for C-O bond homolysis. As a consequence of this observation, we described two new synthetic applications of Nugent's reagent in organic chemistry. The first of these applications is an one-step methodology for deoxygenation-reduction of alcohols, including benzylic and allylic alcohols and 1,2- dihydroxy compounds. Additionally, we have also proved that Ti(III) is capable of mediating carbonyl coupling-olefination. In this sense, and despite the fact that for over 35 years it has been widely accepted that either Ti(II) or Ti(0) was the active species in the reductive process of the McMurry reaction, the mechanistic evidence presented proves the involvement of Ti(III) pinacolates in the deoxygenation step of the herein descnbed Nugent's reagent-mediated McMurry olefination. This observation sheds some light on probably one of the mechanistically more complex transformations in organic chemistry. Finally, we have also proved that both of these processes can be performed catalytically in CpTiCl by using trimethylsilyl chloride (TMSCI) as the final oxygen trap. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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