Ligand-assisted reaction

Despite the extensive utility of osmylation reactions, the mechanism remains controversial - generally focusing on either a concerted [3 + 2] cycloaddition to directly yield the cyclic osmate ester or a two-step mechanism where [2 + 2] cycloaddition forms a 4-membered osmaoxetane which then undergoes a ligand-assisted ring expansion to yield the cyclic osmate ester216 (Scheme 21). 

Complexes involving oxime ligands display a variety of reactivity modes that lead to unusual types of chemical compounds. As far as the oxime chemistry of platinum is concerned, these complexes are involved in facile deprotonation of the OH group with formation of oximato complexes, reduction of Pt(IV) species, Pt(II)-assisted reactions with coordinated allene," alkylation by ketones, oxime-ligand-supported stabilization of Pt(III)—Pt(III) compounds, oxidative conversion into rare nitrosoalkane platinum(II) species, and coupling with organocyanamides. ... 

Lately, a number of papers have dealt with microwave-assisted reactions on palladium-doped A1203. Villemin reported on Stifle, Suzuki, Heck and Trost—Tsuji reactions where potassium fluoride on alumina was used as the base26. The reactions were carried out without solvent or stabilising phosphine ligands in single-mode reactors. The Stifle reactions were noteworthy as the toxic organotin residue remained adsorbed on the solid support, thus allowing a simplified work-up procedure for the otherwise unpleasant, and toxic, stannous by-products. Both the Stifle and the Suzuki reactions could be performed under air. Furthermore, it was noted that with experiments where the... 

Recently, Taillefer et al. reported an Fe/Cu cooperative catalysis in the assembly of N-aryl heterocycles by C—N bond formation [90]. Similarly, Wakharkar and coworkers described the N-arylation of various amines with aryl halides in the presence of Cu—Fe hydrotalcite [91]. Interestingly, Correa and Bolm developed a novel and promising ligand-assisted iron-catalyzed N-arylation of nitrogen nucleophiles without any Cu co-catalysts (Scheme 6.19) [92]. Differently substituted aryl iodides and bromides react with various amides and N-heterocycles. The new catalyst system consists of a mixture of inexpensive FeCl3 and N,N -dimethylethylenediamine (dmeda). Clearly, this research established a useful starting point for numerous future applications of iron-catalyzed arylation reactions. 

The role of alkali metal cations in the [ RuCL(p-cymene) 2l-pseudo-dipepLide-catalysed enantioselective transfer hydrogenation of ketones with propan-2-ol has been examined. Lithium salts were shown to increase the enantioselectivity of the reaction when 2-PrONa or 2-PrOK was used as the base. An alternative reaction mechanism for the pseudo-dipeptide-based systems, in which the alkali metal cation is an important player in the ligand-assisted hydrogen-transfer step, has been proposed.370... 

In an effort to demonstrate the synthetic utility of vinyliodonium salts, small-scale reactions of (4-rm-butyl-1 -cyclohexenyl)phenyliodonium tetrafluoroborate (62) with various nucleophilic species, especially copper(I) reagents, have been conducted125,126. The copper(I)-assisted reactions include the conversions of 62 to 1-cyano-, 1-halo-, 1-alkyl- and 1-phenyl-4-ter r-butylcyclohexenes (equation 215). The alkylation and phenylation of the cyclohexenyl ligand in 62 with lithium diorganocuprates is noteworthy, since the treatment of 62 with H-butyllithium leads to fragmentation of the iodonium ion and affords only a 0.2% yield of 1 -w-butyl-4-terr-butylcyclohexene (equation 216)126. 

In addition to carbenes exerting a strong trans influence (thermodynamic), which may be manifest as a trans effect (kinetic) in ligand substitution reactions, heteroatom-functionalized carbene ligands (with their associated dipolar resonance contributor, Figure 1.16) may assist in the stabilization of transition states of reduced coordination number by electron donation to the metal. 

The possible assistance given to leaving groups by electrophiles in the form of solvent or metal ions represents one part of a ligand replacement reaction normally referred to as SE2(cyclic). Structure 19 shows the interaction at the transition state. It can be seen as simultaneous attack of the electrophile E at the leaving group X and of the... 

A striking exaple of the influence of the Schlenk equilibrium on the progress of reactions of organomagnesium compounds was observed in, what was named, a ligand-assisted nucleophilic addition reaction (LANA), in which the substrate was a lithium quinol alkoxide [29]. In a typical LANA reaction (Scheme 14) the lithium quinol alkoxide is first prepared in situ, after which follows the sequential addition of l,3-dimethyl-3,4,5,6-tetrahydro-2(l//)-pyrimidone (DPMU) and a Grignard reagent. 

Numerous applications of [Cr(NH3)6]3+ and its derivatives to mechanistic studies of conventional or photo-assisted ligand-exchange reactions have been extensively reviewed.7,270-276 Among other common Cr111 complexes, [Cr(NH3)6]3+ has been used for the studies of reactivities of muonium and positronium atoms in aqueous solutions.313-315 Several computational methods, including DFT calculations,316 a combination of molecular mechanics and angular overlap model calculations, or vibrational analysis have been used for the prediction and interpretation of electronic spectra and photochemical properties of [Cr(NH3)6]3+. 

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