A Theoretical Investigation on the Mechanism of the PtCl2-Mediated Cycloisomerization of Heteroatom-Tethered 1,6-Enynes
- 9 October 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 69 (23) , 8018-8023
- https://doi.org/10.1021/jo048828h
Abstract
A mechanistic study based on DFT theoretical calculations for the PtCl2-catalyzed formation of bicyclic adducts from heteroatom tethered 1,6-enynes is reported. Different reaction pathways have been taken into account and the results are discussed. This analysis clearly reveals that the kinetically preferred pathway involves an initial 6-endo-cyclization from a triggered reactant complex by π-complexation of Pt(II) onto the alkyne to form a cyclopropyl platina-carbene intermediate, followed by a [1,2]-hydrogen shift.Keywords
This publication has 12 references indexed in Scilit:
- Reaction of Enol Ethers with Alkynes Catalyzed by Transition Metals: 5exo‐digversus 6endo‐digCyclizations via Cyclopropyl Platinum or Gold Carbene ComplexesChemistry – A European Journal, 2003
- The Behavior of 1,n-Enynes in the Presence of Transition MetalsChemical Reviews, 2002
- Platinum-Catalyzed Cycloisomerization Reactions of EnynesJournal of the American Chemical Society, 2001
- Cyclizations of Enynes Catalyzed by PtCl2 or Other Transition Metal Chlorides: Divergent Reaction PathwaysJournal of the American Chemical Society, 2001
- Non-Metathesis Ruthenium-Catalyzed C−C Bond FormationChemical Reviews, 2001
- Rh-Catalyzed Enyne CycloisomerizationJournal of the American Chemical Society, 2000
- Metallacyclobutane Complexes of the Group Eight Transition Metals: Synthesis, Characterizations, and ChemistryChemical Reviews, 1994
- Thermal decomposition processes for silanolThe Journal of Physical Chemistry, 1990
- Parallel behavior in kinetic and NMR effects: secondary deuterium isotope effects on the alkaline hydrolysis of estersJournal of the American Chemical Society, 1987
- The path of chemical reactions - the IRC approachAccounts of Chemical Research, 1981