Rh-Catalyzed (5+2) Cycloadditions of 3-Acyloxy-1,4-enynes and Alkynes: Computational Study of Mechanism, Reactivity, and Regioselectivity.
The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 25; pp. 9271 - 9275 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
6/26/2013
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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=89366616&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 89366616 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: 6/26/2013 vid: 135 iid: 25 pid: 997 pub: American Chemical Society artinfo: ui: 89366616 10.1021/ja4036785 ppf: 9271 ppct: 4 formats: tig: atl: Rh-Catalyzed (5+2) Cycloadditions of 3-Acyloxy-1,4-enynes and Alkynes: Computational Study of Mechanism, Reactivity, and Regioselectivity. aug: au: Xiufang Xu Peng Liu Xing-zhong Shu Weiping Tang Houk, K. N. affil: Department of Chemistry, Nankai University, Tianjin, 300071, P.R. China Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, United States School of Pharmacy and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53705-2222, United States su: Rhodium catalysts Ring formation (Chemistry) Alkynes Enynes Reactivity (Chemistry) Regioselectivity (Chemistry) Density functional theory Carbon-carbon bonds sug: subj: Rhodium catalysts Ring formation (Chemistry) Alkynes Enynes Reactivity (Chemistry) Regioselectivity (Chemistry) Density functional theory Carbon-carbon bonds ab: The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast to the (5+2) cycloadditions with vinylcyclopropanes (VCPs), in which alkyne inserts into a rhodium-allyl bond, alkyne insertion into a Rh-C(sp) bond is preferred. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity. In the regioselectivity-determining alkyne insertion step, the alkyne substituent prefers to be distal to the forming C-C bond and thus distal to the OAc group in the product. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2013 holdings: @attributes: islocal: N |
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