Carbonyl yields

Substituted Nickel Carbonyl Complexes. The reaction of trimethyl phosphite and nickel carbonyl yields the monosubstituted colorless oil, (CO)2NiP(OCH )2 [17099-58-0] the disubstituted colorless oil, (CO)2Ni[P(OCH )2]2 [16787-28-3] and the trisubstituted white crystalline soHd,... 

Most ring syntheses of this type are of modern origin. The cobalt or rhodium carbonyl catalyzed hydrocarboxylation of unsaturated alcohols, amines or amides provides access to tetrahydrofuranones, pyrrolidones or succinimides, although appreciable amounts of the corresponding six-membered heterocycle may also be formed (Scheme 55a) (73JOM(47)28l). Hydrocarboxylation of 4-pentyn-2-ol with nickel carbonyl yields 3-methylenetetrahy-drofuranone (Scheme 55b). Carbonylation of Schiff bases yields 2-arylphthalimidines (Scheme 55c). The hydroformylation of o-nitrostyrene, subsequent reduction of the nitro group and cyclization leads to the formation of skatole (Scheme 55d) (81CC82). 

The decarbonylation of oxide-supported metal carbonyls yields gaseous products including not just CO, but also CO2, H2, and hydrocarbons [20]. The chemistry evidently involves the support surface and breaking of C - O bonds and has been thought to possibly leave C on the clusters [21]. The chemistry has been compared with that occurring in Fischer-Tropsch catalysis on metal surfaces [20] support hydroxyl groups are probably involved in the chemistry. 

Indirect electrosynthesis of reactive formyl transition metal compounds involves an initial step of reduction of metal carbonyls to radicals followed by transfer of a hydrogen atom from trialkyltin hydrides190. Electroreduction of metal carbonyls yields products of dimerization and loss of CO from the radical anion. Electroreduction in the presence of R3SnH yields the formylmetalcarbonyls ... 

The incorporation of bridging germanium ligands into high-nuclearity transition metal clusters has been accom-plished. Thermal reaction of Ph3GeH with rhodium carbonyl yields a mixture of germanium/rhodium cluster... 

Hashimoto and co-workers, on the other hand, studied the intramolecular reaction between cyclic carbonyl yield and dimethyl acetylenedicarboxylate (DMAD) (Equation (14)). With dirhodium(ii) tetrakis[A-benzene-fused phthaloyl-(A)-valinate] [Rh2(WBPTV)4] 104, high enantioselectivity (68-92% ee) was achieved over a range of diazo substrates.The high level of enantiocontrol provided conclusive evidence that chiral Rh(ii) catalyst is associated with the ylide in the cycloaddition step. 

Of the isomeric aldehydes indicated in Eq. (7.1), the linear aldehyde corresponding to anti-Markovnikov addition is always the main product. The isomeric branched aldehyde may arise from an alternative alkene insertion step to produce the [RCH(Me)Co(CO)3] or [RCH(Me)Rh(CO)(PPh3)2] complexes, which are isomeric to 2 and 8, respectively. Alternatively, hydroformylation of isomerized internal alkenes also give branched aldehydes. The ratio of the linear and branched aldehydes, called linearity, may be affected by reaction conditions, and it strongly depends on the catalyst used. Unmodified cobalt and rhodium carbonyls yield about 3-5 1 mixtures of the normal and iso products. 

Palladium alkoxide complexes are thought to be formed in the reactions of alcohols catalyzed by palladium(II) chloride. These reactions include the oxidation of alcohols, yielding acetals or ketones,137,138 and their carbonylation, yielding esters.139 Alkoxide intermediates are also thought to be involved in the reaction of sulfur dioxide with [PdCl2] suspended in alcohol (equation 15).140,141... 

Carbonyl yields for glycylglycine, methionine, and glycylmethionine are sharply reduced at — 80°C., and a slight additional reduction occurs at... 

C. For glycine a significant increase in carbonyl yield occurs at —80°C., followed by a large decrease on reducing the temperature to... 

C. The same pattern holds for the data on ammonia yields, as one would expect from Equations 1 and 2. The increase at — 80°C. suggests an effect of phase change while the opposed temperature effect at — 196°C. suggests that a different reaction mechanism is controlling at — 196°C. consistent with observations from electron spin resonance studies that different stable-free radicals are observed below — 150°C. for glycine. The low carbonyl yields found for methionine and the peptides at — 80°C. indicate that the low temperature radicals may still be the stable forms at... 

The ketone moiety of unsaturated 5-ketolactones 79 both directs and facilitates the reactivity of diaminopropane toward a Michael reaction at C-3 and amide formation with the lactone carbonyl, yielding 3-substituted diazepinones 80, as shown in Scheme 36 <1996JHC703>. 

One of the most interesting molecular elimination reactions was first discovered by Norrish and Appleyard65 in 1934 and studied further by Bamford and Nor-rish66-69 in papers appearing in 1935 and 1938. These authors found that, on photolysis, aliphatic ketones with hydrogen atoms on carbons in the gamma position to the carbonyl yielded olefins and a methyl ketone. An early example was found in 2-hexanone, viz. 

One step in the industrial refining of nickel is the decomposition of nickel carbonyl (Ni(CO)4) into nickel and carbon monoxide. In a laboratory reaction, 25.0 g nickel carbonyl yielded 5.34 g nickel. 

The hexacarbonyl and substituted carbonyl cations react with a variety of anionic nucleophiles to produce neutral species. The metathetical reaction of metal carbonylate salts with those of the cationic carbonyls yield primarily a mixed metal carbonyl salt however, on warming, anionic attack may cause expulsion of carbon monoxide and the formation of a metal-metal bond (174-176). 

The products of this photoalkylation reaction are 3-alkylated-2-pyrro-lidones and 5-alkylated-2-pyrrolidones (1 2). It is noteworthy that in this reaction the alkylation at the carbon alpha to the nitrogen atom is the predominating reaction, whereas the alkylation at the carbon alpha to the carbonyl yields the minor product of the reaction. Similar results have been obtained in the thermal process (48). The light-induced addition of 2-pyrrolidone to olefins when induced directly leads to traces only of the desired 1 1 adducts. However, the use of acetone as a photosensitizer enables this reaction to proceed in relatively high yields. 

Solid phase synthesis of highly substituted thiophene derivatives 15 using a cyclic malonic acid ester resin 14 was also reported. Highly pure thiophene derivatives were reported to have been prepared by this solid phase synthesis <0314851>. While alkyl or aromatic substitutions on the P position to the carbonyl yielded the corresponding 5-alkyl/aryl substituted 2-acyl aminothiophene, acetaldehyde did not produce the corresponding 2,3- disubstituted thiophene. 

Succinimides and maleimides are accessible via processes analogous to those described for the corresponding anhydrides (see Section 9.4.3.3). Reactions of (COD)2Ni° with either alkenes or alkynes and isocyanates (i.e. heterocumulene analogs of CO2) give azametallacycles that upon carbonylation yield cyclic imides. With alkenes high yields of metallacycles are formed m both simple isocyanates as well as a,(o-diisocyanates. Carbonylation yields are variable, however (Scheme 18). Alkynes give lower metallacycle yields but high yields of die final imide (Scheme 19). ... 

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