Metalation methylene group

The Peterson reaction has two more advantages over the Wittig reaction 1. it is sometimes less vulnerable to sterical hindrance, and 2. groups, which are susceptible to nucleophilic substitution, are not attacked by silylated carbanions. The introduction of a methylene group into a sterically hindered ketone (R.K. Boeckman, Jr., 1973) and the syntheses of olefins with sulfur, selenium, silicon, or tin substituents (D. Seebach, 1973 B.T. Grdbel, 1974, 1977) illustrate useful applications. The reaction is, however, more limited and time consuming than the Wittig reaction, since metallated silicon derivatives are difficult to synthesize and their reactions are rarely stereoselective (T.H. Chan, 1974 ... 

Because the stmcture of 1,3-diketones comprise a methylene group between two activating carbonyls, equiUbrium is shifted toward the enol form. The equihbrium distribution varies with stmcture and solvent (303,306) (Table 13). The enol forms are cycHc and acidic and form covalent, colored, soHd chelates with metals ... 

A five-membered methanide auracycle [Au(C6F5)2(SPPli2CFl2PPh2)]C104 (25) is described with the monosulfonated dppm, obtained after chlorine elimination of [Au (C6F5)2Cl(SPPh2CH2PPh2)j with a silver salt. After deprotonation of the methylene group (26) and later coordination of additional metal centers affords dinuclear and trinuclear methanide derivatives (27, 28) [210]. 

Experimental observations,23 supported by high-level ab initio calculations, 24 indicate that two extreme resonance forms contribute to the general energy of the benzyl cation the aromatic form A, in which the positive charge is concentrated at the methylene group, and the nonaromatic, methylene arenium form B with a sp2 ipso-carbon atom and ring-localized charge (Scheme 3.13). Unlike benzyl cations of the form A, which were isolated and studied, especially by Olah and coworkers,23 compounds represented by the form B remained elusive. Thus, metal complexation... 

As mentioned earlier, metal complexation not only allows isolation of the QM derivatives but can also dramatically modify their reactivity patterns.29o-QMs are important intermediates in numerous synthetic and biological processes, in which the exocyclic carbon exhibits an electrophilic character.30-33 In contrast, a metal-stabilized o-QM can react as a base or nucleophile (Scheme 3.16).29 For instance, protonation of the Ir-T 4-QM complex 24 by one equivalent of HBF4 gave the initial oxo-dienyl complex 25, while in the presence of an excess of acid the dicationic complex 26 was obtained. Reaction of 24 with I2 led to the formation of new oxo-dienyl complex 27, instead of the expected oxidation of the complex and elimination of the free o-QM. Such reactivity of the exocyclic methylene group can be compared with the reactivity of electron-rich enol acetates or enol silyl ethers, which undergo electrophilic iodination.34... 

In cases of complexes bearing an exocyclic double bond directly coordinated to the metal center, the carbons of the double bond usually exhibit coupling with NMR-active metal centers and/or auxiliary ligands.6 14 18 19 The chemical shifts of the quaternary carbon atom vary from 66.976 to 82.2818 ppm, while the methylene group gives rise to signals at 29.16,14 41.91,6 or 51.3418 ppm in the 13C 1H NMR spectra. As one can see, the chemical shift variation is relatively broad and significantly affected by the nature of the metal center. 

N-heterocyclic compounds containing six-membered rings (pyridine and analogues) behave as excellent -acceptors and in turn they provide a rather soft site for metal ion coordination. The 7r-excessive five-membered pyrazole is a poorer 7r-acceptor and a better 7r-donor and it acts as relatively hard donor site. Inclusion of six- and five-membered N-heterocycles like pyridine and pyrazole in one ligand system leads to very attractive coordination chemistry with variations of the electronic properties.555 The insertion of a spacer (e.g., methylene groups) between two heterocycles, which breaks any electronic communication, makes the coordination properties even more manifold. 

The earliest theory, advanced by Fischer and Tropsch in 1926 (84), proposed that the reaction proceeded via formation of intermediate metal carbides which react on the catalyst surface to form methylene groups. It was then suggested that these methylene groups polymerize on the surface to form hydrocarbon chains, which desorb as saturated and unsaturated hydrocarbons. In 1939 Craxford and Rideal expanded the carbide theory, proposing (85), for cobalt-based catalysts, the following reaction sequence ... 

Table 4.10. Optimized bond lengths Rue and Rmh and angles hmc and hmh of transition-metal alkylidenes H ,M=CH2 in Fig. 4.14. (The subscripts i and "o distinguish H—M—H angles that are respectively in plane and out of plane with respect to the methylene group.)...

Cyclopentadienylamine)scandium(2,3-dimethyl-l,3-butadiene) 7 was synthesized in good yield, as shown in Scheme 2. Complex 7 reacted with benzonitrile to form a /rz-imido complex 8, the structure of which was characterized by single crystal X-ray diffraction. This product 8 was proposed to be formed by nitrile insertion followed by an attack of another diene methylene group on the carbon atom of the imido intermediate.3 An unsaturated metal imido species was formed, which easily dimerized to produce 8. However, the yield of 8 was not reported. 

Titanium enolates.1 This Fischer carbene converts epoxides into titanium enolates. In the case of cyclohexene oxide, the product is a titanium enolate of cyclohexanone. But the enolates formed by reaction with 1,2-epoxybutane (equation I) or 2,3-epoxy butane differ from those formed from 2-butanone (Equation II). Apparently the reaction with epoxides does not involve rearrangement to the ketone but complexation of the epoxide oxygen to the metal and transfer of hydrogen from the substrate to the methylene group. 

Metathesis of enynes is another intriguing application in the laboratory. It would seem from the outcome, that it is a completely intramolecular reaction, but if the mechanism involves a metal alkylidene this is not true and the alkylidene group moves on from one substrate molecule to the next, see Figure 16.25. The methylene group moves to the next ring-closed diene. This is a useful tool in organic synthesis [47],... 

A variety of small molecules can be inserted between the two metals in these complexes. The reaction with CH2N2 in CHjClj to insert — CH2- is second order and kinetic parameters for different X s suggest a rate-limiting transfer of an electron pair from the Pt—Pt bond to the methylene group of CH2N2 ... 

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