2026-04-17T14:07:55Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/113462024-06-18T13:49:25Zcom_2072_452955com_2072_2054col_2072_453073

00925njm 22002777a 4500 dc Dachs Soler, Anna author Pla i Quintana, Anna author Parella Coll, Teodor author Solà i Puig, Miquel author Roglans i Ribas, Anna author info:eu-repo/date/embargoEnd/2026-01-01 info:eu-repo/date/embargoEnd/2026-01-01 2011-12 N-Tosyl-linked open-chain yne-ene-yne enediynes 1 and 2 and yne-yne-ene enediynes 3 and 4 have been satisfactorily synthesised. The [2+2+2] cycloaddition process catalysed by the Wilkinson catalyst [RhCl(PPh 3) 3] was tested with the above-mentioned substrates resulting in the production of high yields of the cycloadducts. Enediynes 1 and 2 gave standard [2+2+2] cycloaddition reactions whereas enediynes 3 and 4 suffered β-hydride elimination followed by reductive elimination of the Wilkinson catalyst to give cycloadducts, which are isomers of those that would be obtained by standard [2+2+2] cycloaddition reactions. The different reactivities of these two types of enediyne have been rationalised by density functional theory calculations Financial support from the Spanish MICINN (CTQ2008-05409-C02-02, CTQ2008-03077, CTQ2011-23156, CTQ2011-23121 and CTQ2009-08328) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637) is acknowledged. A. D. thanks the Spanish MEC for a doctoral fellowship. Support for the research of M. S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE http://hdl.handle.net/10256/11346 Reaccions d'addició Addition reactions Funcional de densitat, Teoria del Density functionals Mecanismes de reacció (Química) Reaction mechanisms (Chemistry) Rodi Rhodium Ciclització (Química) Ring formation (Chemistry) Intramolecular [2+2+2] cycloaddition reactions of Yne-ene-yne and Yne-yne-ene enediynes catalysed by Rh I: Experimental and theoretical mechanistic studies