Origins of Regioselectivity and Alkene-Directing Eftects in Nickel-Catalyzed Reductive Couplings of Alkynes and Aldehydes.
The origins of reactivity and regioselectivity in nickel-catalyzed reductive coupling reactions of alkynes and aldehydes were investigated with density functional calculations. The regioselectivities of reactions of simple alkynes are controlled by steric effects, while conjugated enynes and diynes...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 6; pp. 2050 - 2058 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
2/17/2010
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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=48404901&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 48404901 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: 2/17/2010 vid: 132 iid: 6 pid: 997 pub: American Chemical Society artinfo: ui: 48404901 10.1021/ja909562y ppf: 2050 ppct: 8 formats: tig: atl: Origins of Regioselectivity and Alkene-Directing Eftects in Nickel-Catalyzed Reductive Couplings of Alkynes and Aldehydes. aug: au: Peng Liu McCarren, Patrick Ha-Yeon Cheong, Paul Jamison, Timothy F. Houk, K. N. affil: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095 Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 su: Reactivity (Chemistry) Nickel catalysts Alkynes Aldehydes Density functionals sug: subj: Reactivity (Chemistry) Nickel catalysts Alkynes Aldehydes Density functionals ab: The origins of reactivity and regioselectivity in nickel-catalyzed reductive coupling reactions of alkynes and aldehydes were investigated with density functional calculations. The regioselectivities of reactions of simple alkynes are controlled by steric effects, while conjugated enynes and diynes are predicted to have increased reactivity and very high regioselectivities, placing alkenyl or alkynyl groups distal to the forming C-C bond. The reactions of enynes and diynes involve 1,4-attack of the Ni-carbonyl complex on the conjugated enyne or diyne. The consequences of these conclusions on reaction design are discussed. 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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