Transition-Metal-Mediated Oxidative Coupling

As demonstrated in Scheme 5.14, Wong and coworkers also reported several syntheses of hydroxytetraphenylenes utilizing transition-metal-mediated oxidative coupling [40]. 

Scheme 5.13 Transition-metal-mediated oxidative coupling.

PPys synthesized by both oxidative routes are also subject to coupling defects, which drastically reduce sought after properties. To circumvent this problem, transition metal-mediated polymerizations have been explored. Once again, the synthetic inflexibility of the pyrrole moiety has proven to be a formidable obstacle in obtaining such materials. The Stille coupling scheme [12], shown in Scheme 60, has been used to prepare a BOC-substitued PPy 63 with the protecting group subsequently removed by thermolytic treatment to yield unsubstitut-... 

The use of hypervalent iodine reagents in carbon-carbon bond forming reactions is summarized with particular emphasis on applications in organic synthesis. The most important recent methods involve the radical decarboxylative alkylation of organic substrates with [bis(acyloxy)iodo]arenes, spirocyclization of para- and ortho-substituted phenols, the intramolecular oxidative coupling of phenol ethers, and the reactions of iodonium salts and ylides. A significant recent research activity is centered in the area of the transition metal-mediated coupling reactions of the alkenyl-, aryl-, and alkynyliodonium salts. 

Metallacycles have been claimed to play pivotal roles in many transition metal-mediated multi-component coupling reactions [1]. For example, [2 -i- 2 -i- 2] alkyne cyclo-trimerization leading to benzenes - the Reppe reaction - has been considered to proceed via metallacyclopentadiene and elusive metallacycloheptatriene intermediates ("common mechanism ), while metallacyclopentenes have been proposed as intermediates for the [2 -i- 2 -i- 1] cyclo-coupling reactions of an alkyne, an alkene, and CO leading to a cyclopentenone (the Pauson-Khand reaction). A metallacyclic compound - which is defined here as a carbocyclic system with one atom replaced by a transition metal element - can be generally formed by oxidative cyclization of two unsaturated molecules with a low-valent transition metal fragment [2-4]. Alter-... 

Because of the extraordinary strength of the carbon-fluorine bond, transition metal-mediated activation of fluoroalkanes and arenes is not easy to achieve. Nevertheless, activation of the C-F bond in highly electron-deficient compounds such as 2,4,6-trifluoropyrimidine, pentafluoropyridine, or hexafluorobenzene is possible with stoichiometric amounts of bis(triethylphosphano) nickel(O) [101] (Scheme 2.45). More recently Herrmann and coworkers [102] have described a variant of the Kumada-Corriu cross-coupling reaction [103] between fluorobenzene and aryl Grignard compounds which uses catalytic amounts of nickel carbene complexes. Hammett analysis of the relative kinetic rate constants indicated that the reaction proceeds via initial oxidative addition of the fluoroaromatic reactant to the nickel(O) species. 

Many C(sp )—C(sp ) coupling reactions not transition metal-mediated involve the two electron oxidation of ethers or amines to oxocarbenium ions or iminium ions. These are then attacked in an ionic mechanism by in i dM-formed enolates or other carbanion nucleophiles to generate product. As such, they will not be covered in this review. 

PEDOT PSS can be synthesized by (1) oxidative, (2) electrochemical, or (3) transition metal-mediated coupling polymerizations in the presence of a monomeric or polymeric counterion. The synthesis of PEDOT PSS by oxidative polymerization... 

Coupling Reactions to Dienes and Enynes. The silyl bromide (1) participates readily in copper or transition metal-mediated coupling reactions to produce 1,3-butadienes, which are very useful s)mthetic intermediates. For example, 2,3-bis[(trimethylsilyl)methyl]-1,3-butadiene (8), derived from the oxidative dimerization of cuprate (2) (M = Cu) is useful for rapid construction of multicyclic systems via tandem Diels-Alder reactions, as depicted in eq 15 The diene 2-dimethylaminomethyl-3-... 

The synthetic routes to polyarylenes make use of the efficient aryl-aryl bond forming reactions that have been developed over the last century. These come in three categories oxidative coupling, reductive coupling, and transition-metal-mediated organometallic cross-coupling reactions (Scheme 6). Of these oxidative coupling, which is here represented by the Kovacic route to poly(para-phenylene) (PPP), is... 

There are no available data on the formation of hydroperoxides derived from DNA within cells. This is likely explained, at least partly, by the fact that DNA is a poorer target than proteins for OH radical as observed upon exposure of mouse myeloma cells to ionizing radiation . However, indirect evidence for DNA peroxidation within cells may be inferred from the measurement of final degradation products that may derive from thymine and guanine hydroperoxidation as the result of oxidation reactions mediated by OH radical and O2, respectively (Sections n.A.2 and n.E.2). It may be pointed out that the measurement of oxidized bases and nucleosides within DNA has been the subject of intense research during the last decade and accurate methods are now available . This includes DNA extraction that involves the chaotropic Nal precipitation step and the use of desferrioxamine to chelate transition metals in order to prevent spurious oxidation of overwhelming nucleobases to occur . HPLC coupled to electrospray ionization... 

This chapter illustrates that electron-rich transition metal-diene complexes can couple with carbon electrophiles and, thereby, provide unusual methods for carbon-carbon bond formation. These procedures are of interest from a synthetic viewpoint since normally uncomplexed dienes or polyenes are not reactive toward weak carbon electrophiles or, with strong electrophiles, undesirable reactions such as polymerization occur. Furthermore, the metal-mediated route often results in desirable regio- and/or stereo-selectivity. Important to the utility of these methods is the ability to free the organic ligand from the metal. In most instances efficient oxidative procedures have been developed for such cleavage reactions. 

---