sp³-sp² vs sp³-sp³ C-C Site Selectivity in Rh-Catalyzed Ring Opening of Benzocyclobutenol: A DFT Study.
The C-C vs C-C site selectivity in the C-C bond activation in Rh-catalyzed ring opening of benzocyclobutenol was systematically investigated using density functional theory (DFT). The catalytic cycle includes three elementary steps: the proton transfer from the substrate to a rhodium hydroxide, the...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 1; pp. 169 - 179 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
1/8/2014
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| 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=93882887&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 93882887 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: 1/8/2014 vid: 136 iid: 1 pid: 997 pub: American Chemical Society artinfo: ui: 93882887 10.1021/ja407422q ppf: 169 ppct: 10 formats: tig: atl: sp³-sp² vs sp³-sp³ C-C Site Selectivity in Rh-Catalyzed Ring Opening of Benzocyclobutenol: A DFT Study. aug: au: Ding, Lina Naoki Ishida Masahiro Murakami Keiji Morokuma affil: Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan su: Carbon-carbon bonds Ring formation (Chemistry) Benzocyclobutenol Density functional theory Proton transfer reactions Rhodium compounds Hydroxides Scission (Chemistry) sug: subj: Carbon-carbon bonds Ring formation (Chemistry) Benzocyclobutenol Density functional theory Proton transfer reactions Rhodium compounds Hydroxides Scission (Chemistry) ab: The C-C vs C-C site selectivity in the C-C bond activation in Rh-catalyzed ring opening of benzocyclobutenol was systematically investigated using density functional theory (DFT). The catalytic cycle includes three elementary steps: the proton transfer from the substrate to a rhodium hydroxide, the C-C cleavage, and the proton transfer from water onto a carbon forming the final product with regeneration of the rhodium hydroxide. The site selectivity is determined by the C-C cleavage step; the C-C cleavage is favored over the C-C cleavage because the former transition state is stabilized by an interaction between the benzene ring of the substrate and Rh. DMSO, a more polar solvent, reduces the site selectivity as the more polar C-C transition state (TS) is stabilized more than the C-C TS and decreases the advantage of the latter TS. DPPF ligand is bulky, and the steric repulsion on the tighter C-C TS causes the loss of the site selectivity. For the even more crowded Rh(P(t-Bu)) catalyst, one phosphine has to dissociate before the C-C cleavage reaction takes place, and the advantage of the C-C TS is regained for the less crowded RhP(t-Bu) active catalyst. 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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