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Alkenes catalysts, palladium complexes

Secondary amines can be added to certain nonactivated alkenes if palladium(II) complexes are used as catalysts The complexation lowers the electron density of the double bond, facilitating nucleophilic attack. Markovnikov orientation is observed and the addition is anti An intramolecular addition to an alkyne unit in the presence of a palladium compound, generated a tetrahydropyridine, and a related addition to an allene is known.Amines add to allenes in the presence of a catalytic amount of CuBr " or palladium compounds.Molybdenum complexes have also been used in the addition of aniline to alkenes. Reduction of nitro compounds in the presence of rhodium catalysts, in the presence of alkenes, CO and H2, leads to an amine unit adding to the alkene moiety. An intramolecular addition of an amine unit to an alkene to form a pyrrolidine was reported using a lanthanide reagent. [Pg.1001]

The mechanism for the reaction catalyzed by cationic palladium complexes (Scheme 24) differs from that proposed for early transition metal complexes, as well as from that suggested for the reaction shown in Eq. 17. For this catalyst system, the alkene substrate inserts into a Pd - Si bond a rather than a Pd-H bond [63]. Hydrosilylation of methylpalladium complex 100 then provides methane and palladium silyl species 112 (Scheme 24). Complex 112 coordinates to and inserts into the least substituted olefin regioselectively and irreversibly to provide 113 after coordination of the second alkene. Insertion into the second alkene through a boat-like transition state leads to trans cyclopentane 114, and o-bond metathesis (or oxidative addition/reductive elimination) leads to the observed trans stereochemistry of product 101a with regeneration of 112 [69]. [Pg.241]

Addition of diphenyl disulfide (PhS)2 to terminal alkynes is catalyzed by palladium complexes to give l,2-bis(phe-nylthio)alkenes (Table 3)168-172 The reaction is stereoselective, affording the (Z)-adducts as the major isomer. A rhodium(i) catalyst system works well for less reactive aliphatic disulfides.173 Bis(triisopropylsilyl) disulfide adds to alkynes to give (Z)-l,2-bis(silylsulfanyl)alkenes, which allows further transformations of the silyl group to occur with various electrophiles.174,175 Diphenyl diselenide also undergoes the 1,2-addition to terminal alkynes in the presence of palladium catalysts.176... [Pg.752]

The reactions catalyzed by cationic palladium complexes are believed to proceed via a different mechanism (Scheme 67).273 Initially, a cationic silylpalladium(n) species is generated by cr-bond metathesis of the Br-Pd+ with a silylstannane. Subsequently, the alkyne and alkene moieties of the 1,6-diyne successively insert into the Pd-Si bond to form a cationic alkylpalladium(n), which then undergoes bond metathesis with silylstannane to liberate the product and regenerate the active catalyst species, S/-Pd+. [Pg.773]

Recently, another type of catalytic cycle for the hydrosilylation has been reported, which does not involve the oxidative addition of a hydrosilane to a low-valent metal. Instead, it involves bond metathesis step to release the hydrosilylation product from the catalyst (Scheme 2). In the cycle C, alkylmetal intermediate generated by hydrometallation of alkene undergoes the metathesis with hydrosilane to give the hydrosilylation product and to regenerate the metal hydride. This catalytic cycle is proposed for the reaction catalyzed by lanthanide or a group 3 metal.20 In the hydrosilylation with a trialkylsilane and a cationic palladium complex, the catalytic cycle involves silylmetallation of an alkene and metathesis between the resulting /3-silylalkyl intermediate and hydrosilane (cycle D).21... [Pg.816]

The dehalogenation of organic halides by organotin hydrides takes place in most cases with a free-radical mechanism [1, 84, 85], The stereospecific reduction of 1,1-dibromo-l-alkenes with Bu3SnH discovered by Uenishi and coworkers [86-89], however, did not occur in the absence of palladium complexes and did not involve radicals. For the synthesis of (Z)-l-bromo-l-alkenes, [(PPh3)4Pd] proved to be the most effective catalyst which could also be generated in situ. The reaction in Eq. (7) proceeded at room temperature and a wide range of solvents could be used. [Pg.525]

Metal chemical shifts have not found extensive use in relation to structural problems in catalysis. This is partially due to the relatively poor sensitivity of many (but not all) spin 1=1/2 metals. The most interesting exception concerns Pt, which is 33.7% abundant and possesses a relatively large magnetic moment. Platinum chemistry often serves as a model for the catalytically more useful palladium. Additionally, Pt NMR, has been used in connection with the hydrosilyla-tion and hydroformylation reactions. In the former area, Roy and Taylor [82] have prepared the catalysts Pt(SiCl2Me)2(l,5-COD) and [Pt()i-Cl)(SiCl2Me)(q -l,5-COD)]2 and used Pt methods (plus Si and NMR) to characterize these and related compounds. These represent the first stable alkene platinum silyl complexes and their reactions are thought to support the often-cited Chalk-Harrod hydrosilylation mechanism. [Pg.20]

Because of its low acidity, hydrogen cyanide seldom adds to nonactivated multiple bonds. Catalytic processes, however, may be applied to achieve such additions. Metal catalysts, mainly nickel and palladium complexes, and [Co(CO)4]2 are used to catalyze the addition of HCN to alkenes known as hydrocyanation.l67 l74 Most studies usually apply nickel triarylphosphites with a Lewis acid promoter. The mechanism involves the insertion of the alkene into the Ni—H bond of a hydrido nickel cyanide complex to form a cr-alkylnickel complex173-176 (Scheme 6.3). The addition of DCN to deuterium-labeled compound 17 was shown to take place... [Pg.299]

Alkenes. Most Group VIII metals, metal salts, and complexes may be used as catalyst in hydrosilylation of alkenes. Platinum and its derivatives show the highest activity. Rhodium, nickel, and palladium complexes, although less active, may exhibit unique selectivities. The addition is exothermic and it is usually performed without a solvent. Transition-metal complexes with chiral ligands may be employed in asymmetric hydrosilylation 406,422... [Pg.323]

In new studies heteropoly acids as cocatalysts were found to be very effective in combination with oxygen in the oxidation of ethylene.1311 Addition of phosphomo-lybdic acid to a chloride ion-free Pd(II)-Cu(II) catalyst system results in a great increase in catalytic activity and selectivity.1312 Aerobic oxidation of terminal alkenes to methy ketones can be performed with Pd(OAc)21313 or soluble palladium complexes. Modified cyclodextrins accelerates reaction rates and enhance selectivities in two-phase systems under mild conditions.1315 1316... [Pg.527]

Procedure. Hexene (Phillips Petroleum, pure grade, 99% ) was dried over sodium and filtered through a layer of A1203 (Merck, Aktivitatsstufe I) to remove peroxides. The alkene was dissolved in benzene (Baker analyzed) dried over sodium, and the reaction mixture was transferred to the reactor. The complex was placed in the jar and the system was closed. To remove all air dissolved in the liquid phase, the system was evacuated and flushed with hydrogen purified for possible 02 by passing a deoxo catalyst (palladium), under a pressure of 10 atm, and then passing a molecular sieve to remove H20 3 to 5 times under stirring. Adjustments permitted stabilization of the pressure in 1-2 min where the reaction rate was to be measured. [Pg.145]

As previously shown for platinum versus palladium complexes, iridium complexes are generally much less effective catalysts than rhodium ones for the ketonization of alkenes by 02, H202 or ROOH. [Pg.350]

Non-oxidative hydrocarboxylation of alkenes to carboxylic acids with CO and H20 is catalyzed by palladium complexes such as PdCl2(PhCN)2 or PdCl2(PPh3)2, and a-methyl acids predominate in the presence of HC1.374,443 A recent improvement of this reaction consisted of the use of a PdCl2/CuCl2/HCl catalyst under oxidative conditions.377 Almost quantitative yields of a-methyl carboxylic acids and dicarboxylic acids were obtained from terminal alkenes and terminal dialkenes respectively, at room temperature and atmospheric pressure (equation 174).377... [Pg.369]

The rhodium(II) catalysts and the chelated copper catalysts are considered to coordinate only to the carbenoid, while copper triflate and tetrafluoioborate coordinate to both the carbenoid and alkene and thus enhance cyclopropanation reactions through a template effect.14 Palladium-based catalysts, such as palladium(II) acetate and bis(benzonitrile)palladium(II) chloride,l6e are also believed to be able to coordinate with the alkene. Some chiral complexes based on cobalt have also been developed,21 but these have not been extensively used. [Pg.1033]

Oxidation of alkenes to ketones. This palladium complex is an effective catalyst for air oxidation of 1-alkenes to methyl ketones in high yield via a nitro-nitrosyl redox couple. ... [Pg.365]

Heterometal alkoxide precursors, for ceramics, 12, 60-61 Heterometal chalcogenides, synthesis, 12, 62 Heterometal cubanes, as metal-organic precursor, 12, 39 Heterometallic alkenes, with platinum, 8, 639 Heterometallic alkynes, with platinum, models, 8, 650 Heterometallic clusters as heterogeneous catalyst precursors, 12, 767 in homogeneous catalysis, 12, 761 with Ni—M and Ni-C cr-bonded complexes, 8, 115 Heterometallic complexes with arene chromium carbonyls, 5, 259 bridged chromium isonitriles, 5, 274 with cyclopentadienyl hydride niobium moieties, 5, 72 with ruthenium—osmium, overview, 6, 1045—1116 with tungsten carbonyls, 5, 702 Heterometallic dimers, palladium complexes, 8, 210 Heterometallic iron-containing compounds cluster compounds, 6, 331 dinuclear compounds, 6, 319 overview, 6, 319-352... [Pg.118]

In Section 16.5, a few other C,C coupling reactions of alkenes and of aromatic compounds, which contain an sp2—OTf, an sp2—Br, or an sp2—Cl bond, will be discussed because these C,C couplings and the preceding ones are closely related mechanistically. These substrates, however, react with metal-free alkenes. Palladium complexes again serve as the catalysts. [Pg.691]

Sml2 has also been employed as a stoichiometric reductant in deoxygenation processes catalysed by palladium complexes.69 For example, allylic acetates can be reduced by treatment with Sml2 and 2-propanol in the presence of a palladium ) catalyst. Unfortunately, this reduction often generates regioisomeric and stereoisomeric mixtures of alkenes (Scheme 4.54).69... [Pg.65]

Whilst the catalysis begins with Pd°, the combination of Pd" with an alkene and nucleophile results in reduction to Pd°. Accordingly, the catalyst may also be introduced in the form of a divalent palladium complex (typically and conveniently more air stable). [Pg.156]


See other pages where Alkenes catalysts, palladium complexes is mentioned: [Pg.140]    [Pg.7196]    [Pg.98]    [Pg.1035]    [Pg.257]    [Pg.179]    [Pg.182]    [Pg.190]    [Pg.194]    [Pg.439]    [Pg.388]    [Pg.389]    [Pg.392]    [Pg.501]    [Pg.694]    [Pg.241]    [Pg.224]    [Pg.400]    [Pg.59]    [Pg.348]    [Pg.435]    [Pg.60]    [Pg.257]    [Pg.79]    [Pg.56]    [Pg.1290]    [Pg.419]   
See also in sourсe #XX -- [ Pg.285 , Pg.288 , Pg.289 , Pg.296 , Pg.301 ]

See also in sourсe #XX -- [ Pg.285 , Pg.288 , Pg.289 , Pg.296 , Pg.301 ]

See also in sourсe #XX -- [ Pg.6 , Pg.285 , Pg.301 ]




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Alkenes palladium catalysts

Alkenes palladium complexes

Alkenes palladium-nitro complex catalysts

Catalysts alkenes

Complexes alkenes

Palladium alkenes

Palladium catalysts catalyst

Palladium complex catalyst

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