Reductant metals

Reduction of isoindoles with dissolving metals or catalytically occurs in the pyrrole ring. Reduction of indolizine with hydrogen and a platinum catalyst gives an octahydro derivative. With a palladium catalyst in neutral solution, reduction occurs in the pyridine ring but in the presence of acid, reduction occurs in the five-membered ring (Scheme 38). Reductive metallation of 1,3-diphenylisobenzofuran results in stereoselective formation of the cw-1,3-dihydro derivative (Scheme 39) (80JOC3982). 

A convenient method for the preparation of 2-alkenylbis(cyclopentadienyl)zirconium(IV) alkoxides and -trialkylsilyloxides is the reductive metalation of the appropriate alkyl or silyl ethers by means of in situ generated bis(cyclopentadienyl)zirconium(II) 124. 

It is not clear whether the silyl iodide causes activation of only one of the benzyloxy groups, or if a substitution by iodine takes place before reductive metalation. These reagents exhibit a high preference for aldehyde over ketone addition13. 

Figure 4. Direct oxide reduction metal product with residues.

Of these reductant metals, the most commonly used is zinc. The reason is that the zinc halides are more volatile than the parent metal and the chances of codeposition of the halides are minimized. Either chloride or iodide is used, although the iodide, being the most volatile, is usually preferred. The volatility of these halides decreases as one goes from the iodides to the chlorides to the fluorides. The reaction is as follows ... 

Reduction Metal content after reduction (%) d , from x-ray line broadening (A) dvS, fromH2 Metal particle chemisorption size distribution at room temp. from electron (A) micrographs Number of B5 sites per mg of Ni Number of B6 sites per cm2 of Ni surface... 

Allylmetallic reagents The ally] anions obtained by reductive metallation of ally I phenyl sulfides with lithium l-(dimethy amino)naphthalenide (LDMAN, 10, 244) react with a, 3-enals to give mixtures of 1,2-adducts. The regioselectivity can be controlled by the metal counterion. Thus the allyllithium or the allyltitanium compound obtained from either 1 or 2 reacts with crotonaldehyde at the secondary terminus of the allylic system to give mainly the adduct 3. In contrast the allylcerium compound reacts at the primary terminus to form 4 as the major adduct. 

Scheme 22 Reduction/metallation sequences for 1,2-[/r-1,2-o-C6H4(CH2)2)]-1,2-c/oso-C2B10H10.

The alkynyl epoxide 73 undergoes a copper-catalyzed reductive metallation by wBuLi [81, 83]. The resultant allenyllithium compound 74 is a versatile intermediate and reacts with various electrophiles (Scheme 3.37). 

Reductive metallation of aldehydes (but not ketones) by tri-n-butyl-(trimethyisilyl)stannane to yield a-hydroxystannanes is catalysed by tetra-n-butylammonium cyanide [15]. Other phase-transfer catalysts are not as effective and solvents, other than tetrahydrofuran, generally give poorer conversions. Use of a chiral catalyst induced 24% ee with 3-phenylpropanal. 

Another common solvent that contains the oxygen atom easily available for coordination with metal cations is THE. The ability of anion-radicals to remove a proton from the position 2 of THE is sometimes a problem. Dimethyl ether is more stable as a solvent its oxygen atom is also exposed and can coordinate with a metal cation with no steric hindrance from the framing alkyl groups. An added advantage of dimethyl ether is that, because of its low boiling point (-22°C), it can be readily removed after reductive metallation and replaced by the desired solvent. The use of aromatic anion-radicals in dimethyl ether (instead of THE) is well documented (Cohen et al. 2001, references therein). 

The metallothermic reduction of an oxide is a useful preparative method for an actinide metal when macro quantities of the actinide are available. A mixture of the actinide oxide and reductant metal is heated in vacuum at a temperature which allows rapid vaporization of the actinide metal, leaving behind an oxide of the reductant metal and the excess reductant metal, in accord with the following equations ... 

The reductant metal must have the following properties (1) the free energy of formation of the oxide of the reductant has to be more negative than that of the actinide oxide and (2) the vapor pressure of the reductant metal needs to be smaller by several orders of magnitude than that of the actinide metal. This difference in vapor pressure should be at least five orders of magnitude to keep the contamination level of the co-evaporated reductant metal in the product actinide metal below the 10 ppm level. 

Americium, californium, and einsteinium oxides have been reduced by lanthanum metal, whereas thorium has been used as the reductant metal to prepare actinium, plutonium, and curium metals from their respective oxides. Berkelimn metal could also be prepared by Th reduction of Bk02 or Bk203, but the quantity of berkelium oxide available for reduction at one time has not been large enough to produce other than thin foils by this technique. Such a form of product metal can be very difficult to handle in subsequent experimentation. The rate and yield of Am from the reduction at 1525 K of americium dioxide with lanthanum metal are given in Fig. 2. 

Actinide metals with lower vapor pressures (Th, Pa, and U) cannot be obtained by this method since no reductant metal exists which has a sufficiently low vapor pressure and a sufficiently negative free energy of formation of its oxide. For the large-scale production of U, Np, and Pu metals, the calciothermic reduction of the actinide oxide (Section II,A) followed by electrorefining of the metal product is preferred (24). In this process the oxide powder and solid calcium metal are vigorously stirred in a CaCl2 flux which dissolves the by-product CaO. Stirring is necessary to keep the reactants in intimate contact. 

At the present time, when gram to kilogram amounts of either Am isotope are available, the method of choice for the preparation of Am metal is the metallothermic reduction of Am02 with La (or Th) using a pressed pellet of the oxide and the reductant metal. An oxide reduction-metal distillation still system is shown schematically in Fig. 11. Yields of Am metal are typically >90% and purity levels equal or exceed 99.5 at %. Further purification of the product Am metal can be achieved by repeated sublimations under bigh vacuum in a Ta apparatus (Section III,B Fig. 4). A photograph of 2 g of Am metal distilled in a Ta apparatus is given in Fig. 12. 

Fig. 11. An oxide reduction-metal distillation still system.

Dissolving metal reductions were among the first reductions of organic compounds discovered some 130 years ago. Although overshadowed by more universal catalytic hydrogenation and metal hydride reductions, metals are still used for reductions of polar compounds and selective reductions of specific types of bonds and functions. Almost the same results are obtained by electrolytic reduction. 

Conjugated dienes can be prepared from certain ketones via their trisylhydrazones (386) by the Shapiro reaction (equation 102). This involves a reductive metallation to a vinyllithium intermediate, transmetallation, for example, with Cu(I) iodide, and oxidative coupling. ... 

II. REDUCTIVE METAL INSERTION INTO CARBON-HALOGEN BONDS... 

When the halogen in the precursor is exceptionally mobile as an anion, even chloro compounds may give poor yields due to extensive self-destruction. For example, chloromethyl methyl ether can be expediently converted into methoxymethyllithium only if sodium/lithium alloy is used and a carefully elaborated protocol is meticulously followed . In the case of 7-chloronorbomadiene, the lithium/4,4 -di-ferf-butylbiphenyl radical anion has to be employed to further reduce the contact time between 7-norbornadienyllithium and its labile precursor. Many reductive metal insertions into... 

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