Reductive Metallation Processes

When electrophiles other than carbonyl compounds or alkyl halides are employed, the basic a-lithio reagents need to be converted to other organo- 

Nonstereoselective reductive samariations on 2-deoxy glycosides, though of limited synthetic value, are nevertheless of mechanistic interest. However, this type of process does have utility in the preparation of C(2)-oxygenated or C (2)-aminated C-glycosides which is described in Sect. 2.2.3. 

7 s°2Pyr 2Sml2 vN r r Sml2 T ochT L 0CH3 FjC O OH 1 OCHj 

---

A. Reductive Metallation Processes How a Radical Initiation Defines the Stereoselectivity of an Anionic Process... 

Etching is followed by seeding with palladium. The palladium nuclei are inserted into the exposed cavities and are catalytically active in the follow-up chemically reductive metallization process. The plastics used in two-shot molding are generally core-catalytic and require no additional seeding or activation. Only the surface has to be etched open to permit access to the catalysts embedded in the plastic [30]. 

Ammonium ions, tetradecyldimethylbenzyl-liquid—Liquid extraction, 1, 548 Ammonium molybdate, 3,1257 Ammonium nitrate, hydroxyl-as plutonium(IV) reductant Purex process, 6, 949 Amphotericin B metal complexes, 2, 973 a-Amylase zinc, 6, 607 Anabaena spp. 

A. Process Schematic. A schematic of the main process sequence for the conversion of plutonia scrap to high-purity metal is shown in Figure 2. Plutonia scrap is fed to both the direct oxide reduction (DOR) process and the plutonium tetrafluoride production/ reduction process. 

The skull metal and oxide are first completely burned to oxide by heating in air to 400-500°C. The plutonium metal spontaneously burns and is collected as a green Pu03 powder. This oxide is recycled back as feed for Direct Oxide Reduction. This process is normally 100% efficient with only a small plutonium residue showing up in items such as clean-up rags. 

One of the most prominent characteristics of Fe(+2) is its ability to undergo oxidation leading to Fe(+3). This was used by Uchiyama et al. when they reported on Fe(+2)-ate complexes as potent electron transfer catalysts [7, 8]. These ferrates are accessible from FeCl2 and 3 equiv. of MeLi. The Fe(+2/+3) oxidation potential of [Me3Fe(+2)]Li 19 in THF is —2.50 V, thus being in between those of Sml2 (—2.33 V) and Mg (—3.05 V). With these alkyliron-ate complexes it was possible to realize a reductive desulfonylation of various A -sulfonylated amines 20 with different basicity. By using Mg metal to restore the active Fe(+2) species 19 a catalytic reductive desulfonylation process was achieved (Scheme 4). 

Reports of reductive elimination from early transition metals are uncommon. However, Bullock and co-workers have reported the elimination of IMes from [WCp(IMes)(CO)2][B(C Fj) J to form the 2-H-imidazolium salt, during ketone hydrogenation probably via a form of reductive elimination process [38]. 

The reduction smelting process involves the reduction of oxidic sources of metals with carbon in the presence of a flux. The process can generally be represented as ... 

Examples of metals which are prepared by the metallothermic reduction of oxides include manganese, chromium, vanadium, zirconium, and niobium. In a manner similar to the production of magnesium by the Pidgeon process, some of the rare earth metals have been produced by the metallothermic reduction-distillation process. 

The isomerization of allylic alcohols provides an enol (or enolate) intermediate, which tautomerizes to afford the saturated carbonyl compound (Equation (8)). The isomerization of allylic alcohols to saturated carbonyl compounds is a useful synthetic process with high atom economy, which eliminates conventional two-step sequential oxidation and reduction.25,26 A catalytic one-step transformation, which is equivalent to an internal reduction/oxidation process, is a conceptually attractive strategy due to easy access to allylic alcohols.27-29 A variety of transition metal complexes have been employed for the isomerization of allylic alcohols, as shown below. 

The existence of tr-complex intermediates in C-H activation chemistry has been suggested to explain inverse kinetic isotope effects in reductive elimination processes whereby alkanes are formed from alkyl metal hydrides (Scheme 3).9... 

As shown in Figure 1, the next step in the catalytic cycle of carbon dioxide hydrogenation is either reductive elimination of formic acid from the transition-metal formate hydride complex or CT-bond metathesis between the transition-metal formate complex and dihydrogen molecule. In this section, we will discuss the reductive elimination process. Activation barriers and reaction energies for different reactions of this type are collected in Table 3. 

While in most of the reports on SIP free radical polymerization is utihzed, the restricted synthetic possibihties and lack of control of the polymerization in terms of the achievable variation of the polymer brush architecture limited its use. The alternatives for the preparation of weU-defined brush systems were hving ionic polymerizations. Recently, controlled radical polymerization techniques has been developed and almost immediately apphed in SIP to prepare stracturally weU-de-fined brush systems. This includes living radical polymerization using nitroxide species such as 2,2,6,6-tetramethyl-4-piperidin-l-oxyl (TEMPO) [285], reversible addition fragmentation chain transfer (RAFT) polymerization mainly utilizing dithio-carbamates as iniferters (iniferter describes a molecule that functions as an initiator, chain transfer agent and terminator during polymerization) [286], as well as atom transfer radical polymerization (ATRP) were the free radical is formed by a reversible reduction-oxidation process of added metal complexes [287]. All techniques rely on the principle to drastically reduce the number of free radicals by the formation of a dormant species in equilibrium to an active free radical. By this the characteristic side reactions of free radicals are effectively suppressed. 

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. 

---