Metal mediated

Metal Ion-Promoted Reactions of Thiols. Metal ion-promoted reactions of thiols have been reviewed (53). The bulk of the coverage concerns metal ion promoted aspects of sulfur chemistry. The main topics of interest are the formation of sulfenamides, sulfides, and disulfides using metal-mediated reactions. 

To date a number of reactions have been carried out in ionic liquids [for examples, see Dell Anna et al. J Chem Soc, Chem Commun 434 2002 Nara, Harjani and Salunkhe Tetrahedron Lett 43 1127 2002 Semeril et al. J Chem Soc Chem Commun 146 2002 Buijsman, van Vuuren and Sterrenburg Org Lett 3 3785 2007]. These include Diels-Alder reactions, transition-metal mediated catalysis, e.g. Heck and Suzuki coupling reactions, and olefin metathesis reactions. An example of ionic liquid acceleration of reactions carried out on solid phase is given by Revell and Ganesan [Org Lett 4 3071 2002]. 

A unique method to generate the pyridine ring employed a transition metal-mediated 6-endo-dig cyclization of A-propargylamine derivative 120. The reaction proceeds in 5-12 h with yields of 22-74%. Gold (HI) salts are required to catalyze the reaction, but copper salts are sufficient with reactive ketones. A proposed reaction mechanism involves activation of the alkyne by transition metal complexation. This lowers the activation energy for the enamine addition to the alkyne that generates 121. The transition metal also behaves as a Lewis acid and facilitates formation of 120 from 118 and 119. Subsequent aromatization of 121 affords pyridine 122. 

Transition metal-mediated transformations of heterocycles 98MI26, 98MI27. 

Metal-mediated iodocarbocyclization and iodoaminocyclizaton reactions leading to heterocycles 99SL1191. 

Transition metal-mediated syntheses of carbazole derivatives 95MI6. 

As discussed in Section 7.3, conventional free radical polymerization is a widely used technique that is relatively easy to employ. However, it does have its limitations. It is often difficult to obtain predetermined polymer architectures with precise and narrow molecular weight distributions. Transition metal-mediated living radical polymerization is a recently developed method that has been developed to overcome these limitations [53, 54]. It permits the synthesis of polymers with varied architectures (for example, blocks, stars, and combs) and with predetermined end groups (e.g., rotaxanes, biomolecules, and dyes). 

The total synthesis of ( )-estrone [( )-1 ] by Vollhardt et al. is a novel extension of transition metal mediated alkyne cyclotrimeriza-tion technology. This remarkable total synthesis is achieved in only five steps from 2-methylcyclopentenone (19) in an overall yield of 22%. The most striking maneuver in this synthesis is, of course, the construction of tetracycle 13 from the comparatively simple diyne 16 by combining cobalt-mediated and ort/io-quinodimethane cycloaddition reactions. This achievement bodes well for future applications of this chemistry to the total synthesis of other natural products. 

Transition metal-mediated phosphorus-carbon bond cleavage and its relevance to homogeneous catalyst deactivation. P. E. Gorrou, Chem. Rev., 1985,85,171 (109). 

Cu-mediated Ullman reaction has been used for the polymerization of dihaloaryls. For example, see ref. 3. This type of polymerization as well as other transition-metal-mediated reactions that involve radicals in the polymerization process is not included in this chapter. 

Pyridones can also be converted to 2-chloropyridines by exchanging the carbonyl functionality using phosphoroxychloride (POCI3) [72]. A combination of N-halosuccinimides and triphenylphosphine has also been applied to introduce halogens in this position [73]. The carbonyl functionality in 2-pyridones makes these systems reactive towards nucleophiles as well, which add in 1,4-reactions with displacement of halides [74]. The use of transition metal mediated couplings like Heck, and Suzuki have also been successfully applied on halogenated 2-pyridones (d. Scheme 10) [36,75]. 

This chapter has taken the reader through a number of microwave-assisted methodologies to prepare and further functionalize 2-pyridone containing heterocycles. A survey of inter-, intramolecular-, and pericyclic reactions together with electrophilic, nucleophilic and transition metal mediated methodologies has been exemplified. Still, a number of methods remain to be advanced into microwave-assisted organic synthesis and we hope that the smorgasbord of reactions presented in this chapter will inspire to more successful research in this area. 

Abstract A literature overview, up to the end of 2004, of the most important microwave-assisted transition-metal-mediated processes used for the decoration and construction of heterocycles is presented. The emphasis of the chapter lies in the use of palladium-assisted reactions but examples of copper- and nickel-mediated processes are also incorporated. 

Keywords Copper MAOS (Microwave assisted organic synthesis) Nickel Palladium Transition-metal-mediated bond formation... 

It has recently been shown that the transition metal-mediated decoration of the pyrazinone scaffold can greatly benefit from microwave irradi-... 

M-substituted 2-pyridones can be prepared by N-alkylation, under basic conditions (pfCa of the amide proton is 11). The resulting anion can then react on either nitrogen or oxygen depending on the conditions employed [24-27]. Also, several direct methods for the construction of N-substituted 2-pyridones have been reported. Two such examples can be seen in Scheme 3 where the first example (a) is an intramolecular Dieckmann-type condensation [28] and the second (b) is a metal-mediated [2 -I- 2 + 2] reaction between alkynes with isocyanates [29,30]. 

Ehses M, Romerosa A, Peruzzini M (2002) Metal-Mediated Degradation and Reaggregation of White Phosphorus. 220 107-140... 

Metal-Mediated Degradation and Reaggregation of White Phosphorus... 

Delmonte AJ, Dowdy ED, Watson DJ (2004) Development of Transition Metal-Mediated Cyclopropanation Reaction. 6 97-122 Demonceau A, see Noels A (2004) 11 155-171 Derien S, see Dixneuf PH (2004) 11 1-44... 

Department of Metal-Mediated Synthesis Debye Research Institute Utrecht University Padualaan 8... 

Scheme 6 Chain propagation in transition-metal-mediated NCA polymerization...

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