Vinyl- and Divinylcyclopentadienes by Rhodium-Catalyzed Condensation of Alkynes with Cross-Conjugated Amino Metallahexatrienes [= (1-Amino-1,3-butadien-2-yl)carbene Complexes] (M = Cr, W)

Aumann, Rudolf; Göttker‐Schnetmann, Inigo; Fröhlich, Roland; Meyer, Oliver

doi:10.1002/(sici)1099-0690(199910)1999:10<2545::aid-ejoc2545>3.0.co;2-a

Cited by 40 publications

(2 citation statements)

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“…The first example in which a Rh catalyst had been successfully applied to enhance the reactivity of a Fischer carbene complex was reported by Aumann and co-workers in the reaction at rt between cross-conjugated metallahexatrienes 49 and alkynes to form vinylcyclopentadienes 50 catalyzed by [(cod)RhCl] 2 (Scheme ) 19 …”

Section: Rh-catalyzed Transmetalation Reactionsmentioning

confidence: 99%

“…The first example in which a Rh catalyst had been successfully applied to enhance the reactivity of a Fischer carbene complex was reported by Aumann and coworkers in the reaction at rt between cross-conjugated metallahexatrienes 49 and alkynes to form vinylcyclopentadienes 50 catalyzed by [(cod)RhCl] 2 (Scheme 19). 26 The thermal (noncatalyzed) condensation of alkynes with 4-amino-1-chroma-1,3-butadienes structurally related to 49 was a known process. 27 However, the reaction applies only to chromium but not to tungsten complexes, requires temperatures of 50-80 °C, and is strongly dependent on the substituents and conditions.…”

Section: Rh-catalyzed Transmetalation Reactionsmentioning

confidence: 99%

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Catalytic Transmetalation from Group 6 Fischer Carbene Complexes: An Emerging Powerful Tool in Organic Synthesis

2004

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The chemistry of metal carbene complexes has experienced an enormous development in the past decades. Despite this fact, the use of transition metals as catalysts in reactions involving group 6 Fischer carbene complexes was virtually neglected. Here, we describe how the reactivity of these compounds can be enhanced or modified in the presence of catalytic amounts of a transition metal, leading to new forms of reactivity and others offering clear advantages in terms of efficiency over the uncatalyzed reactions. The key step for these reactions is the transmetalation from the stoichiometric metal carbene reagent to the catalyst. This process generates a new metal-carbene complex that leads to enhanced reactivity of new reaction modes. Two examples of Fischer carbene complexes obtained by transmetalation to Pd and Cu have been isolated during the last 2 years, showing the flexibility if the mechanistic hypothesis for these reactions. The work presented in this Account shows how an area, which was practically unexplored 5 years ago, has emerged as a new and powerful field of research.

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Section: Rh-catalyzed Transmetalation Reactionsmentioning

confidence: 99%

Section: Rh-catalyzed Transmetalation Reactionsmentioning

confidence: 99%