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Rhodium vinyls

Addition of a rhodium carbenoid to an alkyne leads to a cyclopropene derivative. In an intramolecular context, the fused cyclopropene moiety is unstable and undergoes ring opening to generate a rhodium vinyl carbenoid entity, which can then undergo cyclopropanation or cyclopropena-tion, carbon hydrogen insertion, and ylide generation. This is illustrated... [Pg.276]

Phenol synthesis.1 Reaction of 1 with a cyclopropenc (2) forms a rhodium vinyl carbcnoid (a) that reacts with a terminal alkync (3) to form an oxepine 4 and a phenol 5. On treatment with HC1 4 rearranges to the phenol 5 in practically quantitative yield. [Pg.326]

Olefin isomerization can be catalyzed by a number of catalysts such as molybdenum hexacarbonyl [13939-06-5] Mo(CO)g. This compound has also been found to catalyze the photopolymerization of vinyl monomers, the cyclization of olefins, the epoxidation of alkenes and peroxo species, the conversion of isocyanates to carbodiimides, etc. Rhodium carbonylhydrotris(triphenylphosphine) [17185-29-4] RhH(CO)(P(CgH )2)3, is a multifunctional catalyst which accelerates the isomerization and hydroformylation of alkenes. [Pg.172]

In general, hydrogenolysis of vinylic compounds is favored by platinum and hydrogenation by ruthenium and rhodium 31,55,59,72,106). In the reduction of 4-methyl-1-cyclohexenyl ether, the order of decreasing hydrogenolysis to give methylcyclohexane was established as Pt Ir > Rh > Os Ru = Pd (52). [Pg.41]

The catalyst exerts some influence on the bonds broken in hydrogenolysis of saturated cyclopropanes (775), but in vinyl and alkylidene cyclopropanes the effect is pronounced. Platinum or palladium are used frequently. In one case, Nishimura s [124a) catalyst, rhodium-platinum oxide (7 3), worked well where platinum oxide failed (.75). An impressive example of the marked influence of catalyst is the hydrogenation of the spirooctane 42, which,... [Pg.174]

Approximately 2.5 million tons of acetic acid is produced each year in the United States for a variety of purposes, including preparation of the vinyl acetate polymer used in paints and adhesives. About 20% of the acetic acid synthesized industrially is obtained by oxidation of acetaldehyde. Much of the remaining 80% is prepared by the rhodium-catalyzed reaction of methanol with carbon monoxide. [Pg.752]

Intermediate 37 can be transformed into ( )-thienamycin [( )-1)] through a sequence of reactions nearly identical to that presented in Scheme 3 (see 22— 1). Thus, exposure of /(-keto ester 37 to tosyl azide and triethylamine results in the facile formation of pure, crystalline diazo keto ester 4 in 65 % yield from 36 (see Scheme 5). Rhodium(n) acetate catalyzed decomposition of 4, followed by intramolecular insertion of the resultant carbene 3 into the proximal N-H bond, affords [3.2.0] bicyclic keto ester 2. Without purification, 2 is converted into enol phosphate 42 and thence into vinyl sulfide 23 (76% yield from 4).18 Finally, catalytic hydrogenation of 23 proceeds smoothly (90%) to afford ( )-thienamycin... [Pg.262]

Vinyl boranes add to conjugated ketones in the presence of a rhodium catalyst (with high asymmetric induction in the presence of BINAP) 7 Alkynyl-boranes also add to conjugated ketones, in the presence of... [Pg.1032]

In the presence of metal catalysts such as rhodium compounds, aldehydes can add directly to alkenes to form ketones. The reaction of co-alkenyl aldehydes with rhodium catalyst leads to cyclic ketones, with high enantioselectivity if chiral ligands are employed. Aldehydes also add to vinyl esters in the presence of hyponitrites and thioglycolates. ° ... [Pg.1038]

Much of the early work into the rhodium(II)-catalysed formation of oxazoles from diazocarbonyl compounds was pioneered by the group of Helquist. They first reported, in 1986, the rhodium(II) acetate catalysed reaction of dimethyl diazomalonate with nitriles.<86TL5559, 93T5445, 960S(74)229> A range of nitriles was screened, including aromatic, alkyl and vinyl derivatives with unsaturated nitriles, cyclopropanation was found to be a competing reaction (Table 3). [Pg.10]

The rhodium-mediated reaction of 69 with 2,3-dihydrofuran (a formal dipolar cycloaddition of a cyclic diazo dicarbonyl compound with a vinyl ether) yields 70. Corrqiound 70 can be transformed in a number of steps to 71 a,b <96TL2391>. [Pg.141]

The syntheses and spectroscopic and electrochemical characterization of the rhodium and iridium porphyrin complexes (Por)IVI(R) and (Por)M(R)(L) have been summarized in three review articles.The classical syntheses involve Rh(Por)X with RLi or RMgBr, and [Rh(Por) with RX. In addition, reactions of the rhodium and iridium dimers have led to a wide variety of rhodium a-bonded complexes. For example, Rh(OEP)]2 reacts with benzyl bromide to give benzyl rhodium complexes, and with monosubstituted alkenes and alkynes to give a-alkyl and fT-vinyl products, respectively. More recent synthetic methods are summarized below. Although the development of iridium porphyrin chemistry has lagged behind that of rhodium, there have been few surprises and reactions of [IrfPorih and lr(Por)H parallel those of the rhodium congeners quite closely.Selected structural data for rr-bonded rhodium and iridium porphyrin complexes are collected in Table VI, and several examples are shown in Fig. 7. ... [Pg.295]

Hydroformylation of vinyl acetate to give mainly the branched product in >90% ee has been achieved using a rhodium catalyst containing binaphthol and phosphine ligands anchored to polystyrene. [Pg.119]

As corroborated by deuterium labeling studies, the catalytic mechanism likely involves oxidative dimerization of acetylene to form a rhodacyclopen-tadiene [113] followed by carbonyl insertion [114,115]. Protonolytic cleavage of the resulting oxarhodacycloheptadiene by the Bronsted acid co-catalyst gives rise to a vinyl rhodium carboxylate, which upon hydrogenolysis through a six-centered transition structure and subsequent C - H reductive elimina-... [Pg.103]

Rhodium(II) pivalate has also been recommended for the cyclopropanation of vinyl halides with ethyl diazoacetate 78). As Table 8 shows, yields with this catalyst are far higher and reaction conditions milder than with copper. Failures are noted,... [Pg.97]

Table 8. Cyclopropanation of vinyl halides with ethyl diazoacetate in the presence of rhodium(Il) pivalate (Rhpiv) or copper... Table 8. Cyclopropanation of vinyl halides with ethyl diazoacetate in the presence of rhodium(Il) pivalate (Rhpiv) or copper...
Most of the reports on Rh-catalyzed asymmetric hydroformylation are concerned with asymmetric hydroformylation of vinyl aromatics, which are model substrates of interest to the pharmaceutical industry. In 1993 and 1995, reports were published describing the state of the art in hydroformylation with both rhodium and platinum systems.80,81 310 Two reports appeared in 1999 and 2000 on carbonylation and rhodium asymmetric hydroformylation respectively.311,345... [Pg.171]


See other pages where Rhodium vinyls is mentioned: [Pg.578]    [Pg.62]    [Pg.265]    [Pg.252]    [Pg.889]    [Pg.578]    [Pg.62]    [Pg.265]    [Pg.252]    [Pg.889]    [Pg.133]    [Pg.471]    [Pg.48]    [Pg.52]    [Pg.455]    [Pg.121]    [Pg.801]    [Pg.940]    [Pg.1039]    [Pg.61]    [Pg.49]    [Pg.124]    [Pg.96]    [Pg.104]    [Pg.106]    [Pg.118]    [Pg.147]    [Pg.162]    [Pg.164]    [Pg.171]    [Pg.172]    [Pg.174]    [Pg.245]   
See also in sourсe #XX -- [ Pg.265 ]




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