Electrophilic addition metals

Silicon and tin are both subject to ipra-replacement by electrophiles, via an electrophilic addition/metal elimination mechanism analogous to other aromatic substitutions, but at a much faster rate than the corresponding replacement of hydrogen. /pra-substitutions also take place on heterocycles and, in the case of electron-rich systems, probably via the same type of mechanism. 

SECTION 6.4. ELECTROPHILIC ADDITIONS INVOLVING METAL IONS... 

The mechanism through which catalytic metal carbene reactions occur is outlined in Scheme 2. With dirhodium(II) catalysts the open axial coordination site on each rhodium serves as the Lewis acid center that undergoes electrophilic addition to the diazo compound. Lewis bases that can occupy the axial coor-... 

In favor of a dihydrogen intermediate, the following should be noted (i) the addition of HX molecules to OsHCl(CO)(P Pr3)2 is a useful synthetic route for dihydrogen compounds (vide infra), (ii) the electrophilic character of the dihydrogen complexes has been demonstrated,38 and (iii) the addition of electrophiles to metal alkynyl complexes is a general method of preparing vinylidene compounds.39... 

In view of the similarities between the bonding models for carbene and carbyne complexes it is not surprising that similar patterns of reactivity should be observed for these compounds. Thus nucleophilic and electrophilic additions to the metal-carbon triple bond are anticipated under appropriate circumstances, and both orbital and electrostatic considerations will be expected to play a role. 

The effect of metal basicity on the mode of reactivity of the metal-carbon bond in carbene complexes toward electrophilic and nucleophilic reagents was emphasized in Section II above. Reactivity studies of alkylidene ligands in d8 and d6 Ru, Os, and Ir complexes reinforce the notion that electrophilic additions to electron-rich compounds and nucleophilic additions to electron-deficient compounds are the expected patterns. Notable exceptions include addition of CO and CNR to the osmium methylene complex 47. These latter reactions can be interpreted in terms of non-innocent participation of the nitrosyl ligand. 

It was proposed that electrophilic addition of a metal carbene rather than direct insertion or fragmentation of an initially formed 2-azabicyclo[3.1.0]hex-3-ene accounts for the formal insertion products 239) (Scheme 33). 

With an electrophilic transition metal complex, it is believed that the hydration of an alkyne occurs through a trans-addition of water to an 72-alkyne metal complex (Scheme 15, path A),380 although the m-pathway via hydroxymetallation has also been proposed (path B).381,382 However, distinguishing between the two pathways is difficult due to the rapid keto-enol tautomerization that renders isolation of the initial water adduct challenging. 

The synthesis of polyhalide salts, R4NX , used in electrophilic substitution reactions, are described in Chapter 2 and H-bonded complexed salts with the free acid, R4NHX2, which are used for example in acid-catalysed cleavage reactions and in electrophilic addition reactions with alkenes, are often produced in situ [33], although the fluorides are obtained by modification of method I.I.I.B. [19, 34], The in situ formation of such salts can inhibit normal nucleophilic reactions [35, 36]. Quaternary ammonium chlorometallates have been synthesized from quaternary ammonium chlorides and transition metal chlorides, such as IrClj and PtCl4, and are highly efficient catalysts for phase-transfer reactions and for metal complex promoted reactions [37]. 

Electron-rich olefins are nucleophilic and therefore subject to thermal cleavage by various electrophilic transition metal complexes. As the formation of tetraaminoethylenes, i.e., enetetramines, is possible by different methods, various precursors to imidazolidin-2-ylidene complexes are readily available. " Dimerization of nonstable NHCs such as imidazolidin-2-ylidenes is one of the routes used to obtain these electron-rich olefins [Eq. (29)]. The existence of an equilibrium between free NHC monomers and the olefinic dimer was proven only recently for benzimidazolin-2-ylidenes. In addition to the previously mentioned methods it is possible to deprotonate imidazolidinium salts with Grignard reagents in order to prepare tetraaminoethylenes. " The isolation of stable imidazolidin-2-ylidenes was achieved by deprotonation of the imidazolidinium salt with potassium hydride in THF. ... 

Scheme 14 Typical nucleophilic and electrophilic additions on metal-allenylidenes...

Another type of Cinchona alkaloid catalyzed reactions that employs azodicarbo-xylates includes enantioselective allylic amination. Jprgensen [51-53] investigated the enantioselective electrophilic addition to aUyhc C-H bonds activated by a chiral Brpnsted base. Using Cinchona alkaloids, the first enantioselective, metal-free aUyhc amination was reported using alkylidene cyanoacetates with dialkyl azodi-carboxylates (Scheme 12). The product was further functionalized and used in subsequent tandem reactions to generate useful chiral building blocks (52, 53). Subsequent work was applied to other types of allylic nitriles in the addition to a,P-unsaturated aldehydes and P-substituted nitro-olefins (Scheme 13). 

BMIM]BF4 was applied to a Suzuki reaction. The active catalyst was a trico-ordinated [Pd(PPh3)2(Ar)][X] complex that formed after oxidative addition of aryl halide to [Pd(0)(PPh3)4] 211). The hydrophobic ionic liquid does not compete with the unsaturated organic substrate for the electrophilic active metal center. 

Subramaniam, 1988]. Hydrochlorination, usually carried out at about 10°C, proceeds by electrophilic addition to give the Markownikoff product with chlorine on the tertiary carbon (Eq. 9-33) [Golub and Heller, 1964 Tran and Prud homme, 1977]. Some cyclization of the intermediate carbocation (XXVI) also takes place (Sec. 9-7). The product, referred to as rubber hydrochloride, has low permeability to water vapor and is resistant to many aqueous solutions (hut not bases or oxidizing acids). Applications include packaging film laminates with metal foils, paper, and cellulose films, although it has been largely replaced by cheaper packaging materials such as polyethylene. 

---