Synthesis of 9-Alkylidene-9H-fluorenes by a Novel, Palladium-Catalyzed Cascade Reaction of Aryl Halides and 1-Aryl-1-alkynes
- 6 October 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 66 (22), 7372-7379
- https://doi.org/10.1021/jo010561o
Abstract
In the presence of a palladium catalyst and NaOAc, aryl iodides react with 1-aryl-1-alkynes to afford 9-alkylidene-9H-fluorenes in good yields. The products from this reaction are highly dependent on the base employed. This process appears to involve (1) oxidative addition of the aryl iodide to Pd(0), (2) alkyne insertion, (3) rearrangement of the resulting vinylic palladium intermediate to an arylpalladium species, and (4) aryl−aryl coupling with simultaneous regeneration of the Pd(0) catalyst. Consistent with this mechanism is the fact that 9-alkylidene-9H-fluorenes can also be prepared by the Pd-catalyzed rearrangement of 1,1-diaryl-2-iodo-1-alkenes.Keywords
This publication has 30 references indexed in Scilit:
- Palladium-catalyzed annulationPublished by Walter de Gruyter GmbH ,1999
- Palladium-catalyzed annulationJournal of Organometallic Chemistry, 1999
- Palladium catalysed cascade alkyne-arene vinylation/alkylation approach to polyfused heterocyclesTetrahedron Letters, 1996
- Transition Metal-Catalyzed Carbocyclizations in Organic SynthesisChemical Reviews, 1996
- On the regioselectivity of Pd catalyzed intramolecular carbametalationsTetrahedron Letters, 1993
- A new synthesis of substituted fulvenesJournal of the American Chemical Society, 1990
- One-step construction of fused tricyclic and tetracyclic structures from acyclic precursors via cyclic carbopalladationJournal of the American Chemical Society, 1990
- Reactions of cyclopalladated compounds and alkynes: New pathways for organic synthesis?Recueil des Travaux Chimiques des Pays-Bas, 1990
- Metal-promoted cyclization. 25. Palladium-catalyzed cascade carbometalation of alkynes and alkenes as an efficient route to cyclic and polycyclic structuresJournal of the American Chemical Society, 1989
- Transition metal-mediated cycloaddition reactions of alkynes in organic synthesisChemical Reviews, 1988