期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 50, 页码 13124-13135出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201802546
关键词
alkenes; copper; cross-coupling; density functional calculations; reaction mechanisms
资金
- Ministerio de Economia y Competitividad (MINECO) (Spain) [CTQ2017-87889-P]
- Gobierno de Aragon (Spain) [E97]
- Gobierno de Aragon-Fondo Social Europeo (Spain)
- Universidad de Zaragoza
- Fundacion Bancaria Ibercaja
- Fundacion CAI
The Cu-mediated synthesis of tetrasubstituted ole-fins by the addition of an acetate group and a thiolate to an unactivated internal alkyne is described. The reaction is fully stereoselective, because only the E alkene is obtained. If the alkyne is asymmetric, the reaction also shows a very high degree of regioselectivity. The mechanism of the reaction is elucidated by DFT methods, which show that it takes place through Cu-stabilized radical species. Calculations highlight the crucial role of the dimeric copper(II) diacetate in the process, as it generates the active species in which the sulfur center has an incipient thiyl radical character and accepting, through a series of changes in the oxidation states of the two copper centers, the two electrons released in the addition of two nucleophiles to the alkyne.
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