Intramolecular bond activation

As can be seen in the scheme below, insertion reactions of aldehydes to the C-H bond of aromatic ketimines by using a rhenium catalyst provided benzo[c]furans via a mechanism involving consecutive steps of C-H bond activation, insertion of aldehyde, intramolecular nucleophilic cyclization, reductive elimination, and elimination of aniline <06JA12376>. 

Another important reaction principle in modem organic synthesis is carbon-hydrogen bond activation [159]. Bergman, Ellman, and coworkers have introduced a protocol that allows otherwise extremely sluggish inter- and intramolecular rhodium-catalyzed C-H bond activation to occur efficiently under microwave heating conditions. In their investigations, these authors found that heating of alkene-tethered benzimidazoles in a mixture of 1,2-dichlorobenzene and acetone in the presence of di-//-... 

Intramolecular arylation of G-H bonds gives cyclic aromatic compounds. In this intramolecular arylation, the carbon-palladium cr-bond is first formed by the oxidative addition of Pd(0) species and then the resulting electrophilic Pd(n) species undergoes the intramolecular G-H bond activation leading to the formation of the palladacycle, which finally affords the cyclic aromatic compounds via reductive elimination.87 For example, the fluoroanthene derivative is formed by the palladium-catalyzed reaction of the binaphthyl triflate, as shown in Scheme 8.88 This type of intramolecular arylation is applied to the construction of five- and six-membered carbocyclic and heterocyclic systems.89 89 89 ... 

Studies of intramolecular C-H bond activation reactions at Pt(II) (and Pd(II)) leading to cyclometalated products have typically found that these reactions are facilitated by ancillary ligands that can easily dissociate (20,21). In the absence of any weakly bonded ligand, unusually... 

The intermediate case is that the antibonding level of the molecule broadens across the Fermi level, as shown in Fig. A.13. It becomes partially filled, and consequently the intramolecular bond is weakened. The relevance for catalysis is that this type of chemisorption weakens (or activates in catalytic language) the... 

Figure A.15 Energy diagram for the adsorption of a simple diatomic molecule on a d-metal. Chemisorption orbitals are constructed from both the bonding and the antibonding levels of the molecule. As the latter becomes partially occupied, the intramolecular bond of the adsorbate has been activated.

Intramolecular C-N bond coupling in arylazides via C-H bond activation catalyzed by [Ir(COD)(OMe)]2 was recently reported [131]. The intermediate iridium nitrenoid complex (50) formed after the extrusion of dinitrogen is proposed as a reactive species, which can cleave the benzylic C-H bond to yield indoline derivatives (31). 

Trifluoroethanol (TFE, CE3CH2OH) also demonstrates high H-bond activity. The dyad system in which a radical and electron-donor parts are linked directly undergoes intramolecular electron transfer on substitution of TEE for toluene as a solvent. The transition was interpreted as a marked effect of hydrogen bonding (or reversible protonation) of the anionic R-0 structure with TFE (Nishida et al. 2005). Scheme 5.17 depicts this transition. 

Transition metals are used extensively as reforming catalysts and the variation in the catalytic activity can be determined by the differences in the strength of the adsorbate-surface interaction with various metals. One of the fundamental properties of a metal surface is in fact its ability to bond or to interact vflth surrounding atoms and molecules. The bonding ability determines the state of the metal surface when exposed to a gas or liquid and it determines the ability of the surface to act as a catalyst. During catalysis, the surface forms chemical bonds to the reactants and it helps in this way the breaking of intramolecular bonds and the formation of new bonds. 

Scheme 38 Inter-intramolecular carbopalladations involving formal C-H bond activation of an arene moiety7 ...

This then was the first report of a compound in which alkyl C—H bond activation by a transition metal had occurred. In the solid state, this equilibrium is also in favor of the hydrido complex (V), and its crystal structure has recently been determined (15). It shows compound V to be a dimer (VI), the oxidative addition of the methyl group of a ligand on each ruthenium atom being to a second ruthenium atom. Presumably one reason why this occurs is because the product of intramolecular ring closure would contain a highly strained three-membered Ru—P—C ring (i.e., in monomer V). 

Pyrrole and indole rings can also be constructed by intramolecular addition of nitrogen to a multiple bond activated by metal ion complexation. Thus, 1-aminomethyl-l-alkynyl carbinols (obtained by reduction of cyanohydrins of acetylenic ketones) are cyclized to pyrroles by palladium(II) salts. In this reaction the palladium(II)-complexed alkyne functions as the electrophile with aromatization involving elimination of palladium(II) and water (Scheme 42) (81TL4277). 

Ito and co-workers have also used the Pd(OAc)2/t-alkyl isocyanide catalyst to affect the double silylation of carbon-carbon multiple bonds in an intramolecular system to yield silacarbocycles.59 Alkenes or alkynes that are tethered to a disilanyl group through a carbon chain, an ether linkage, or an amine functionality undergo intramolecular addition of the disilane moiety to the multiple bond. Activation of the disilane by the presence of electron-withdrawing groups on silicon is not necessary for the reaction to... 

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