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Olefin stoichiometric

One remarkable application of carbene complexes is the combination of olefin metathesis with carbonyl olefination. If a given substrate has both C-C and C-0 double bonds, it might be possible to realize with a given carbene complex olefin metathesis to yield a new carbene complex, followed by an intramolecular carbonyl olefination step. As emphasized above, because of the irreversibility of the carbonyl olefination, stoichiometric amounts of carbene complex will be required. [Pg.134]

Over 35 years ago, Richard F. Heck found that olefins can insert into the metal-carbon bond of arylpalladium species generated from organomercury compounds [1], The carbopalladation of olefins, stoichiometric at first, was made catalytic by Tsutomu Mizoroki, who coupled aryl iodides with ethylene under high pressure, in the presence of palladium chloride and sodium carbonate to neutralize the hydroiodic acid formed (Scheme 1) [2], Shortly thereafter, Heck disclosed a more general and practical procedure for this transformation, using palladium acetate as the catalyst and tri-w-butyl amine as the base [3], After investigations on stoichiometric reactions by Fitton et al. [4], it was also Heck who introduced palladium phosphine complexes as catalysts, enabling the decisive extension of the ole-fination reaction to inexpensive aryl bromides [5],... [Pg.277]

To quantitate the wastefulness or economy of a reaction, researchers consider its characteristic atom utilization. This number is a fraction reckoned by dividing the molecular weight of the desired product by the sum of the molecular weights of all the products and by-products. The closer this fraction approaches unity the better. In principle, it equals 1 in the case of addition reactions, for example the bromination of an olefin. Stoichiometric reactions, because they form more products than only the desired one, are less efficient. [Pg.202]

In the chlorohydrin route, generally preferred in the epoxidation of C3-C4 olefins, stoichiometric amounts of sodium or calcium chlorides are produced by the dehydrohalogenation of intermediate halohydrins. Chlorinated organic by-products, such as halogen ethers and dichlorides, are formed as well in the process, fur er increasing the quantity of wastes. [Pg.59]

The other important direct alkylation processes involve reaction of electron-rich olefinic compounds with either tin metal or stannous chloride (tin(II) chloride) in the presence of stoichiometric amounts of hydrogen chloride (22). Butyl acrylate (R = C Hg) was used commercially in this process to prepare the estertin or P-carboalkoxyethyltin chlorides as iHustrated in the foUowing. [Pg.547]

Olefin distribution in the Albemarle stoichiometric process tends to foUow the Poisson equation, where is the mole fraction of alkyl groups in whichp ethylene units have been added, and n is the average number of ethylene units added for an equal amount of aluminum. [Pg.437]

However, the composition of the mixture can be controlled to some extent by the correct choice of olefin and reaction conditions. For example, the production of tertiary phosphines can be maximi2ed by conducting the reaction at relatively low phosphine pressures, 1.5 MPa (200 psi), and using a 20—30% stoichiometric excess of a straight-chained olefin as in the synthesis of tributylphosphine [988-40-3] by reaction with 1-butene [106-98-9]. [Pg.318]

Ritter Reaction (Method 4). A small but important class of amines are manufactured by the Ritter reaction. These are the amines in which the nitrogen atom is adjacent to a tertiary alkyl group. In the Ritter reaction a substituted olefin such as isobutylene reacts with hydrogen cyanide under acidic conditions (12). The resulting formamide is then hydroly2ed to the parent primary amine. Typically sulfuric acid is used in this transformation of an olefin to an amine. Stoichiometric quantities of sulfate salts are produced along with the desired amine. [Pg.200]

Olefin Isomerization. Some olefins can be isomerized in the presence of metal carbonyls. The carbonyl can act as a catalyst or a stoichiometric reagent in the reaction (137). [Pg.69]

The Wilkinson hydrogenation cycle shown in Figure 3 (16) was worked out in experiments that included isolation and identification of individual rhodium complexes, measurements of equiUbria of individual steps, deterrnination of rates of individual steps under conditions of stoichiometric reaction with certain reactants missing so that the catalytic cycle could not occur, and deterrnination of rates of the overall catalytic reaction. The cycle demonstrates some generally important points about catalysis the predominant species present in the reacting solution and the only ones that are easily observable by spectroscopic methods, eg, RhCl[P(CgH 2]3> 6 5)312 (olefin), and RhCl2[P(CgH )2]4, are outside the cycle, possibly in virtual equiUbrium with... [Pg.164]

The Jacobsen-Katsuki epoxidation reaction is an efficient and highly selective method for the preparation of a wide variety of structurally and electronically diverse chiral epoxides from olefins. The reaction involves the use of a catalytic amount of a chiral Mn(III)salen complex 1 (salen refers to ligands composed of the N,N -ethylenebis(salicylideneaminato) core), a stoichiometric amount of a terminal oxidant, and the substrate olefin 2 in the appropriate solvent (Scheme 1.4.1). The reaction protocol is straightforward and does not require any special handling techniques. [Pg.29]

The stoichiometric reaction of lithium dialkylcuprates in diethyl ether with a-substituted /J-methylallyl sulfoxides and sulfones gives the /-substitution product with high regio- and E stereoselectivity82. The reaction provides a stereoselective method for the synthesis of trisubsti-tuted (TQ-olefins. [Pg.878]

In the peaking process of the Ethyl Corporation, the catalytic single-step process and the stoichiometric two-step process are combined. The result is an olefin mixture with a narrowed molecular weight distribution [25]. In this combined process low molecular weight olefins (preferably n-butene-1) obtained by a single-step process are used as displacement olefins (instead of ethylene) in the second step of the stoichiometric two-step Alfen process. Table 7 shows the composition of an olefinic mixture produced by the combination process of the Ethyl Corporation. The values in Table 7 show that the olefin mixtures of the... [Pg.12]

Larock has developed a new catalyst system for the Pd-catalyzed cyclization of olefinic tosylamides. Whereas typical conditions require either stoichiometric amounts of Pd(II) salts or catalytic amounts of Pd(II) in the presence of benzoquinone as a reoxidant, the new catalyst system utilizes catalytic Pd(OAc)2 under an atmosphere of O2 in DMSO with no additional reoxidant <96JOC3584>. Although o-vinylic tosylamides 76 can be cyclized to Af-tosylindoles 77 using this catalyst system, PdCla/benzoquinone is more effective for such cyclizations. Interestingly, in the case of o-allylic tosylanilides, the cyclization can be modulated to afford either dihydroindole or dihydroquinoline products. In a related approach involving a common 7i-aUyl Pd-intermediate, 2-iodoanilines were coupled with vinylic cyclopropanes or cyclobutanes in the presence of a Pd catalyst to afford dihydroindoles <96T2743>. [Pg.105]

Hegedus et al. have thoroughly studied the homogeneous hydroamination of olefins in the presence of transition metal complexes. However, most of these reactions are either promoted or assisted, i.e. are stoichiometric reactions of an amine with a coordinated alkene [98-101] or, if catalytic, give rise to the oxidative hydroamination products, as for example in the cyclization of o-allylanilines to 2-alkylindoles [102, 103], i.e. are relevant to Wacker-type chemistry [104]. [Pg.97]

Mono-, di-, and trisubstituted olefins undergo osmium-catalyzed enantioselective dihydroxylation in the presence of the (R)-proline-substituted hydroquinidine 3.9 to give diols in 67-95% yields and in 78-99% ee.75 Using potassium osmate(VI) as the catalyst and potassium carbonate as the base in a tm-butanol/water mixture as the solvent, olefins are dihydroxylated stereo- and enantioselectively in the presence of 3.9 and potassium ferricyanide with sodium chlorite as the stoichiometric oxidant the yields and enantiomeric excesses of the... [Pg.58]

Subsequently, stoichiometric asymmetric aminohydroxylation was reported.78 Recently, it was found by Sharpless79 that through the combination of chloramine-T/Os04 catalyst with phthalazine ligands used in the asymmetric dihydroxylation reaction, catalytic asymmetric aminohydroxylation of olefins was realized in aqueous acetonitrile or tert-butanol (Scheme 3.3). The use of aqueous rerr-butanol is advantageous when the reaction product is not soluble. In this case, essentially pure products can be isolated by a simple filtration and the toluenesulfonamide byproduct remains in the mother liquor. A variety of olefins can be aminohydroxylated in this way (Table 3.1). The reaction is not only performed in aqueous medium but it is also not sensitive to oxygen. Electron-deficient olefins such as fumarate reacted similarly with high ee values. [Pg.59]

TFA) was used in place of TFAA, non-A-protected aziridines were obtained as the products.144 Although the reactions of conjugated trans-olefins show high enantioselectivity, a stoichiometric amount of the nitrido-Mnv species is required. [Pg.228]

DHQD-CL or DHQ-CL) was used as the chiral auxiliary.175,176 However, the enantioselectivity observed under catalytic conditions was inferior to that observed under stoichiometric conditions. The addition of triethylammonium acetate, which increases the rate of hydrolysis of the Osvm-glycolate intermediate, improved enantioselectivity. A further improvement in enantioselectivity was brought about by the slow addition of substrates (Scheme 44).177 These results indicated that the hydrolysis of the Osvm-glycolate intermediate (57) was slow under those conditions and (57) underwent low enantioselective dihydroxylation (second cycle). Thus, Sharpless et al. proposed a mechanism of the dihydroxylation including a second cycle (Scheme 45).177 Slow addition reduces the amount of unreacted olefin in the reaction medium and suppresses the... [Pg.233]


See other pages where Olefin stoichiometric is mentioned: [Pg.127]    [Pg.128]    [Pg.284]    [Pg.209]    [Pg.1614]    [Pg.128]    [Pg.23]    [Pg.127]    [Pg.128]    [Pg.284]    [Pg.209]    [Pg.1614]    [Pg.128]    [Pg.23]    [Pg.297]    [Pg.437]    [Pg.437]    [Pg.438]    [Pg.317]    [Pg.135]    [Pg.137]    [Pg.119]    [Pg.57]    [Pg.676]    [Pg.687]    [Pg.195]    [Pg.216]    [Pg.324]    [Pg.34]    [Pg.61]    [Pg.46]    [Pg.311]    [Pg.325]    [Pg.64]    [Pg.65]    [Pg.219]    [Pg.243]    [Pg.240]    [Pg.122]   
See also in sourсe #XX -- [ Pg.134 , Pg.165 , Pg.167 ]

See also in sourсe #XX -- [ Pg.406 ]




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Stoichiometric olefin metathesis

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