2024-03-28T15:45:15Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1760942020-12-13T09:10:00Zcom_10261_33com_10261_5col_10261_286
Iridium(I)-Catalyzed Intramolecular Cycloisomerization of Enynes: Scope and Mechanistic Course
Fernández, David F.
Rodrigues, C. A. B.
Calvelo, M.
Gulías, Moisés
Mascareñas, José L.
López, Fernando
Ministerio de Economía, Industria y Competitividad (España)
Xunta de Galicia
Catalysis
Cyclization
Iridium
Hydrocarbonation
C−H activation
We report an Ir(I)-catalyzed cycloisomerization methodology that provides access to carbocyclic systems bearing exo-alkene moieties from alkynyl-equipped acyclic precursors. The method relies on the C-H activation of olefinic and (hetero)aromatic C(sp)-H bonds, followed by an exocyclization to a tethered alkyne, and provides interesting cyclic diene products that are amenable of further elaboration. Importantly, DFT calculations suggests that, in contrast to related hydrocarbonations of alkenes in which either migratory insertions or C-C reductive eliminations have been suggested to be rate-determining, in our reactions, the energetic barrier of these steps is lower than that of the previous C-H activation.
2019-02-14T12:34:10Z
2019-02-14T12:34:10Z
2018
2019-02-14T12:34:10Z
artículo
ACS Catalysis 8: 7397-7402 (2018)
http://hdl.handle.net/10261/176094
10.1021/acscatal.8b02139
http://dx.doi.org/10.13039/501100010198
http://dx.doi.org/10.13039/501100010801
eng
Sí
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SAF2016-76689-R
closedAccess
American Chemical Society