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"Formal" and Standard Ruthenium-Catalyzed [2 + 2 + 2] Cycloaddition Reaction of 1,6-Diynes to Alkenes: A Mechanistic Density Functional Study.
- Source :
-
Journal of Organic Chemistry . 2/15/2008, Vol. 73 Issue 4, p1320-1332. 13p. 2 Diagrams, 2 Charts, 11 Graphs. - Publication Year :
- 2008
-
Abstract
- "Formal" and standard Ru(II)-catalyzed [2 + 2 + 2] cycloaddition of 1,6-diynes 1 to alkenes gave bicyclic 1,3-cyclohexadienes in relatively good yields. The neutral Ru(II) catalyst was formed in situ by mixing equimolecular amounts of [Cp*Ru(CH3CN)3IPF6 and Et4NCI; Two isomeric bicyclic 1,3-cyclohexadienes 3 and 8 were obtained depending on the cyclic or acyclic nature of the alkene partner. Mechanistic studies on the Ru catalytic cycle revealed a clue for this difference: (a) when acyclic alkenes were used, linear coupling of 1,6-diynes with alkenes was observed giving 1,3,5-trienes 6 as the only initial reaction products, which after a thermal disrotatory 6e-π electrocyclization led to the final 1,3-cyclohexadienes 3 as probed by NMR studies. This cascade process behaved as a formal Ru-catalyzed [2 + 2 + 2] cycloaddition. (b) With cyclic alkenes, the standard Ru-catalyzed [2 + 2 + 21 cycloaddition occurred, giving the bicyclic 1,3-cyclohexadienes 8 as reaction-products. A complete catalytic cycle for the formal and standard Ru-catalyzed [2 + 2 + 2] cycloaddition of acetylene and cyclic and acyclic alkenes with the Cp*RuCl fragment has been proposed and discussed based on DFT/B3LYP calculations. The most likely mechanism for these processes would involve the formation of ruthenacycloheptadiene intermediates XXIII or XXVII depending on the alkene nature. From these complexes, two alternatives could be envisioned: (a) a reductive elimination in the case of cyclic alkenes 7 and (b) a β-elimination followed by reductive elimination to give 1,3,5-hexatrienes 6 in the case of acyclic alkenes. Final 6e-π electrocyclization of 6 gave 1,3-cyclohexadienes 3. [ABSTRACT FROM AUTHOR]
- Subjects :
- *CATALYSIS
*RUTHENIUM
*RING formation (Chemistry)
*ALKENES
*DENSITY functionals
Subjects
Details
- Language :
- English
- ISSN :
- 00223263
- Volume :
- 73
- Issue :
- 4
- Database :
- Academic Search Index
- Journal :
- Journal of Organic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 31124372
- Full Text :
- https://doi.org/10.1021/jo702239v