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Allylic compound

Reactions of nickel carbonyl with allylic halides have been studied by Chiusoli (16). At 100° and 50 atm of carbon monoxide in the presence of [Pg.6]

At ordinary pressure only small amounts of acid are isolated instead, dimerization of the allyl groups occurs (76, 77) (Eq. 6) [Pg.7]

It has been proposed (76) that carbonylation proceeds according to Eqs. (7), (8), and (9) [Pg.7]

Carbonylation of allylic halides in the presence of an acetylene occurs with insertion of one acetylene molecule, according to Eq. (10) (76) [Pg.7]

Phenol is obtained as a by-product and is probably formed in a cyclic transition state (VIII), Eq. (11) [Pg.7]

The carbonylation of allylic compounds by transition metal complexes is a versatile method for synthesizing unsaturated carboxylic acid derivatives (Eq. 11.22) [64]. Usually, palladium complexes are used for the carbonylation of allylic compounds [65], whereas ruthenium complexes show characteristic catalytic activity in allylic carbonylation reactions. Cinnamyl methyl carbonate reacts with CO in the presence of a Ru3(CO)i2/l,10-phenanthroline catalyst in dimethylformamide (DMF) to give methyl 4-phenyl-3-butenoate in excellent yield (Eq. 11.23) [66]. The regioselectivity is the same as in the palladium complex-catalyzed reaction. However, when ( )-2-butenyl methyl carbonate is used as a substrate, methyl ( )-2-methyl-2-butenoate is the major product, with the more sterically hindered carbon atom of the allylic group being carbo-nylated (Eq. 11.24). This regioselectivity is characteristic of the ruthenium catalyst [66]. [Pg.284]

The insertion of CO into an allylic carbon-sulfur bond was first achieved using either a palladium or ruthenium catalyst (Eq. 11.25) [67]. [Pg.284]

Oxidative cydocarbonylation of 1,1-disubstituted allylic alcohols was accomplished with the RuCl2(PPh3)3 catalytic system to form 2(5H)-furanones (Eq. 11.26). [Pg.285]

The presence of CO and an excess amount of allyl acetate, which is a hydrogen acceptor, is essential in this respect [68]. [Pg.285]

When homoallyl alcohols are treated under analogous reaction conditions, the carbonylation reaction does not occur rather, a characteristic carbon-carbon bond cleavage occurs to give ketones and alkenes. During this reaction, /3-carbon elimination occurs to give the products. The CO pressure is cmcial for suppressing deactivation of the catalyst and stabilizing the active species by coordination to the metal center (Eq. 11.27) [69]. [Pg.285]


Formation of a Tr-allylpalladium complex 29 takes place by the oxidative addition of allylic compounds, typically allylic esters, to Pd(0). The rr-allylpal-ladium complex is a resonance form of ir-allylpalladium and a coordinated tt-bond. TT-Allylpalladium complex formation involves inversion of stereochemistry, and the attack of the soft carbon nucleophile on the 7r-allylpalladium complex is also inversion, resulting in overall retention of the stereochemistry. On the other hand, the attack of hard carbon nucleophiles is retention, and hence Overall inversion takes place by the reaction of the hard carbon nucleophiles. [Pg.15]

TT-Aliylpalladium chloride reacts with a soft carbon nucleophile such as mal-onate and acetoacetate in DMSO as a coordinating solvent, and facile carbon-carbon bond formation takes place[l2,265], This reaction constitutes the basis of both stoichiometric and catalytic 7r-allylpalladium chemistry. Depending on the way in which 7r-allylpalladium complexes are prepared, the reaction becomes stoichiometric or catalytic. Preparation of the 7r-allylpalladium complexes 298 by the oxidative addition of Pd(0) to various allylic compounds (esters, carbonates etc.), and their reactions with nucleophiles, are catalytic, because Pd(0) is regenerated after the reaction with the nucleophile, and reacts again with allylic compounds. These catalytic reactions are treated in Chapter 4, Section 2. On the other hand, the preparation of the 7r-allyl complexes 299 from alkenes requires Pd(II) salts. The subsequent reaction with the nucleophile forms Pd(0). The whole process consumes Pd(ll), and ends as a stoichiometric process, because the in situ reoxidation of Pd(0) is hardly attainable. These stoichiometric reactions are treated in this section. [Pg.61]

Several Pd(0) complexes are effective catalysts of a variety of reactions, and these catalytic reactions are particularly useful because they are catalytic without adding other oxidants and proceed with catalytic amounts of expensive Pd compounds. These reactions are treated in this chapter. Among many substrates used for the catalytic reactions, organic halides and allylic esters are two of the most widely used, and they undergo facile oxidative additions to Pd(0) to form complexes which have o-Pd—C bonds. These intermediate complexes undergo several different transformations. Regeneration of Pd(0) species in the final step makes the reaction catalytic. These reactions of organic halides except allylic halides are treated in Section 1 and the reactions of various allylic compounds are surveyed in Section 2. Catalytic reactions of dienes, alkynes. and alkenes are treated in other sections. These reactions offer unique methods for carbon-carbon bond formation, which are impossible by other means. [Pg.125]

Stereochemical features in the oxidative addition and the elimination of /3-hydrogen of cyclic and acyclic alkenes are different. The insertion (palladation) is syn addition. The syn addition (carbopalladation) of R—Pd—X to an acyclic alkene is followed by the syn elimination of 3-hydrogen to give the trans-a ksne 6, because free rotation of 5 is possible with the acyclic alkene. On the other hand, no rotation of the intermediate 7 is possible with a cyclic alkene and the syn elimination of /3-hydrogen gives the allylic compound 8 rather than a substituted alkene. [Pg.128]

Reactions of Allylic Compounds via 7r-Allylpalladium Complexes Catalyzed by Pd(0)... [Pg.290]

Reaction Patterns and Various Allylic Compounds Used for Catalytic Reactions... [Pg.290]

In addition, a catalytic version of Tt-allylpalladium chemistry has been devel-oped[6,7]. Formation of the Tr-allylpalladium complexes by the oxidative addition of various allylic compounds to Pd(0) and subsequent reaction of the complex with soft carbon nucleophiles are the basis of catalytic allylation. After the reaction, Pd(0) is reformed, and undergoes oxidative addition to the allylic compounds again, making the reaction catalytic.-In addition to the soft carbon nucleophiles, hard carbon nucleophiles of organometallic compounds of main group metals are allylated with 7r-allylpalladium complexes. The reaction proceeds via transmetallation. These catalytic reactions are treated in this chapter. [Pg.290]

In addition to the catalytic allylation of carbon nucleophiles, several other catalytic transformations of allylic compounds are known as illustrated. Sometimes these reactions are competitive with each other, and the chemo-selectivity depends on reactants and reaction conditions. [Pg.291]

Mainly allylic esters are used as the substrates for the catalytic reactions. In addition, the allylic compounds shown are known to react with Pd(0) to form TT-allylpalladium complexes. Even allylic nitro compounds[8,9] and sul-fones[KM2] are used for the allylation. The reactivities of these allylic compounds arc very different. [Pg.291]

Asymmetric allylation of carbon nucleophiles has been carried out extensively using Pd catalysts coordinated by various chiral phosphine ligands and even with nitrogen ligands, and ee > 90% has been achieved in several cases. However, in most cases, a high ee has been achieved only with the l,3-diaryl-substitiitcd allylic compounds 217, and the synthetic usefulness of the reaction is limited. Therefore, only references are cited[24,133]. [Pg.319]

Wylation under neutral conditions. Reactions which proceed under neutral conditions are highly desirable, Allylation with allylic acetates and phosphates is carried out under basic conditions. Almost no reaction of these allylic Compounds takes place in the absence of bases. The useful allylation under neutral conditions is possible with some allylic compounds. Among them, allylic carbonates 218 are the most reactive and their reactions proceed under neutral conditions[13,14,134], In the mechanism shown, the oxidative addition of the allyl carbonates 218 is followed by decarboxylation as an irreversible process to afford the 7r-allylpalladium alkoxide 219. and the generated alkoxide is sufficiently basic to pick up a proton from active methylene compounds, yielding 220. This in situ formation of the alkoxide. which is a... [Pg.319]

Dienes and allylarcncs can be prepared by the Pd-catalyzcd coupling of allylic compounds with hard carbon nucleophiles derived from alkenyl and aryl compounds of main group metals. Allylic compounds with various leaving groups can be used. Some of them are unreactive with soft nucleophiles, but... [Pg.345]

Allylic metal compounds useful for further transformations can be prepared by Pd-catalyzed reactions of allylic compounds with bimetallic reagents. By this transformation, umpolung of nucleophilic 7r-allylpalladium complexes to electrophilic allylmetal species can be accomplished. Transfer of an allyl moiety from Pd to Sn is a typical umpolung. [Pg.353]

When allylic compounds are treated with Pd(0) catalyst in the absence of any nucleophile, 1,4-elimination is a sole reaction path, as shown by 492, and conjugated dienes are formed as a mixture of E and Z isomers[329]. From terminal allylic compounds, terminal conjugated dienes are formed. The reaction has been applied to the syntheses of a pheromone, 12-acetoxy-1,3-dode-cadiene (493)[330], ambergris fragrance[331], and aklavinone[332]. Selective elimination of the acetate of the cyanohydrin 494 derived from 2-nonenal is a key reaction for the formation of the 1,3-diene unit in pellitorine (495)[333], Facile aromatization occurs by bis-elimination of the l,4-diacetoxy-2-cyclohex-ene 496[334],... [Pg.356]

BU3P. A rapid redox reaction takes place to yield the active Pd(0) species and tributylphosphine oxide. The Pd(0) thus generated is a phosphine-free cata-lyst[341]. Severe reaction conditions are necessary, or no reaction takes place, when Pd2(dba)3 is used in the elimination reaction of cyclic allylic compounds with an excess of -Bu3P[342]. [Pg.361]

The Pd-catalyzed hydrogenolysis of allylic compounds by various hydrides gives alkenes. From terminal allylic compounds, either 1-alkenes or 2-alkenes are formed depending on the hydride sources [360a]. [Pg.366]

In addition to the preparation of l-alkenes, the hydrogenolysis of allylic compounds with formate is used for the protection and deprotection of carboxylic acids, alcohols, and amines as allyl derivatives (see Section 2.9). [Pg.368]

Various terminal allylic compounds are converted into l-alkenes at room temperature[362]. Regioselective hydrogenolysis with formate is used for the formation of an exo-methylene group from cyclic allylic compounds by the formal anti thermodynamic isomerization of internal double bonds to the exocyclic position[380]. Selective conversion of myrtenyl formate (579) into /9-pinene is an example. The allylic sulfone 580 and the allylic nitro compound... [Pg.368]


See other pages where Allylic compound is mentioned: [Pg.6]    [Pg.293]    [Pg.295]    [Pg.301]    [Pg.305]    [Pg.307]    [Pg.315]    [Pg.318]    [Pg.319]    [Pg.320]    [Pg.321]    [Pg.325]    [Pg.327]    [Pg.331]    [Pg.333]    [Pg.335]    [Pg.339]    [Pg.340]    [Pg.343]    [Pg.345]    [Pg.347]    [Pg.349]    [Pg.351]    [Pg.355]    [Pg.359]    [Pg.361]    [Pg.363]    [Pg.365]    [Pg.366]    [Pg.366]    [Pg.367]    [Pg.367]    [Pg.369]   
See also in sourсe #XX -- [ Pg.41 , Pg.42 , Pg.43 ]

See also in sourсe #XX -- [ Pg.93 ]

See also in sourсe #XX -- [ Pg.2 ]




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5-Allyl-derivatives from 5-bromo compounds

8-Lactams, a-methylenesynthesis allyl organometallic compounds

A-Alkoxyaldimines reaction with allyl organometallic compounds

A-Allyl compounds

Acetals, allylic reaction with organocopper compounds

Acetophenone reaction with allylic organometallic compounds

Acrylic and Allylic Compounds

Active methylene compounds coupling with allylic

Active methylene compounds with allylic esters

Aldehydes allylic boron compounds

Aldehydes, p-alkoxy reaction with allyl organometallic compounds

Aldimines, N-propylreaction with allyl organometallic compounds

Aldimines, a-alkoxyreaction with allyl organometallic compounds

Alkali-metal compounds, allyl

Allyl Palladium Species from Allylic Compounds

Allyl acetates reactions with carbonyl compounds

Allyl alcohols via organocerium compounds

Allyl compound copolymerization

Allyl compounds

Allyl compounds

Allyl compounds Subject

Allyl compounds heterogeneous catalysis

Allyl compounds hydrogenation

Allyl compounds metal complexes

Allyl compounds nucleophilic addition

Allyl compounds nucleophilic displacement

Allyl compounds photochemistry

Allyl compounds, carbene insertion into

Allyl compounds, carbene insertion into bonds

Allyl compounds, deuterated

Allyl compounds, metal-containing

Allyl compounds, nucleophilic

Allyl compounds, nucleophilic substitution

Allyl halides with organocopper compounds

Allyl halides with organotin compounds

Allyl halides with organozinc compounds

Allyl hetero compounds

Allyl hetero compounds 1,3-heteroatom-hydrogen transposition reaction

Allyl hetero compounds reduction

Allyl metal compounds

Allyl metal compounds protonation

Allyl metal compounds reactions with aldehydes

Allyl metal compounds reactions with electrophiles

Allyl nickel compounds

Allyl nitro compounds

Allyl nitro compounds reduction

Allyl organometallic compounds

Allyl organometallic compounds 1.3- asymmetric induction

Allyl organometallic compounds 3 + 2] cycloaddition reactions

Allyl organometallic compounds C stereocenters

Allyl organometallic compounds Cram selectivity

Allyl organometallic compounds Knoevenagel reaction

Allyl organometallic compounds chelation control

Allyl organometallic compounds chiral

Allyl organometallic compounds conventional auxiliaries

Allyl organometallic compounds diastereoselectivity

Allyl organometallic compounds enantioselective

Allyl organometallic compounds reactions with 8-phenylmenthylA-methoxyiminoacetate

Allyl organometallic compounds reactions with a-phenylaldimine

Allyl organometallic compounds reactions with aldimines

Allyl organometallic compounds reactions with chiral C=N electrophiles

Allyl organometallic compounds reactions with gem-amino ethers

Allyl organometallic compounds reactions with glyoxylate aldimines

Allyl organometallic compounds reactions with imines

Allyl organometallic compounds relative diastereoselectivity

Allyl organometallic compounds reviews

Allyl phosphoryl compounds

Allyl phosphoryl compounds synthesis

Allyl phosphoryl compounds via rearrangement

Allyl reaction with carbonyl compounds

Allyl sulfur compounds

Allyl sulphur compounds

Allyl-lead compounds

Allylation 1,3-dicarbonyl compounds

Allylation allylic nitro compounds

Allylation and Propargylation of Carbonyl Compounds

Allylation of active methylene compound

Allylation of carbonyl compounds

Allylation of carbonyl compounds mediated

Allylation of carbonyl compounds mediated by indium

Allylation of carbonyl compounds mediated by tin

Allylation of carbonyl compounds mediated by zinc

Allylation of imines and related compounds

Allylation of nitro compounds

Allylation preparation of 1,4-dicarbonyl compounds

Allylation reaction of carbonyl compounds

Allylation reactions with carbonyl compounds

Allylations carbonyl compounds

Allylic acetates reactions with carbonyl compounds

Allylic alcohol carbonyl compounds

Allylic alcohols coupling with carbonyl compounds

Allylic alcohols, synthesis from compounds

Allylic aromatic compounds

Allylic borinate compounds

Allylic compounds 2- acrylonitrile

Allylic compounds Allylsilanes

Allylic compounds From epoxides

Allylic compounds Lithium-Ethylamine

Allylic compounds Methyllithium

Allylic compounds Nickel

Allylic compounds Other methods

Allylic compounds Selenium dioxide

Allylic compounds Sodium borohydride

Allylic compounds Tetrakis palladium

Allylic compounds Wohl-Ziegler reaction

Allylic compounds amines

Allylic compounds carbonylation

Allylic compounds catalytic reactions

Allylic compounds conjugated diene preparation

Allylic compounds hydrogenolysis

Allylic compounds microbial oxidation

Allylic compounds oxidation

Allylic compounds oxidations, copper®) chloride

Allylic compounds phosphates

Allylic compounds reactions

Allylic compounds reductions, lithium aluminum hydride

Allylic compounds stoichiometric reactions

Allylic compounds transposition

Allylic compounds, cross-metathesis

Allylic compounds, hydrogenolysi

Allylic compounds, lithium aluminum hydride

Allylic compounds, nucleophilic attack

Allylic derivatives 3-hetero-substituted compounds

Allylic derivatives carbonylation, acetate compounds

Allylic halides compounds

Allylic halides reaction with vinyltin compounds

Allylic ketone compounds

Allylic lithium compounds

Allylic nitro compounds

Allylic nitro compounds denitration

Allylic nitro compounds elimination

Allylic nitro compounds preparation

Allylic nitro compounds rearrangement

Allylic nitro compounds, reduction

Allylic organolithium compounds

Allylic organometallic compounds

Allylic organozinc compounds, addition

Allylic organozinc compounds, addition reactions

Allylic phosphorus compounds

Allylic substitutions propargyl compounds

Allylic zinc compounds

Aluminum, triethylreaction of allylic anions with carbonyl compounds

Aluminum, triethylreaction of allylic anions with carbonyl compounds regioselectivity

Azacycloheptane, 2,2-disubstituted from allyl organometallic compounds

Biomimetic reduction allylic compounds

Butyraldehyde, 3-methoxy a-alkoxyaldimines derived from reaction with allyl organometallic compounds

C-Glycosyl compounds allyl tin radical

Carbon monoxide allylic compounds

Carbon nucleophiles allylic compounds. Tsuji-Trost reaction

Carbonates, allylic, coupling compounds

Carbonyl compounds Sakurai allylation reaction

Carbonyl compounds allylation

Carbonyl compounds allylic oxidation

Carbonyl compounds allylic silanes

Carbonyl compounds formation, enolate allylation

Carbonyl compounds reactions with allylic sulfinyl carbanions

Carbonylation of allylic compounds

Catalytic Reactions of Allylic Compounds

Catalytic and Stoichiometric Reactions of Allylic Compounds

Chiral compounds allylic amination

Copper compounds allylation

Copper compounds allylic displacement

Cross-coupling allylic compounds

Cyclic compounds allylic halides

Cyclohexylamine, V-methyl-4-z-butylreaction with allyl organometallic compounds

Cyclopentenone synthesis allylic compounds

Diastereofacial selectivity allyl organometallic compounds

Dimetallic compounds allylation

Dynamic allylic compounds

Electrochemical reduction allylic compounds

Electrophilic allyl derivatives zinc compounds

Electrophilic compounds allyl ester transformation

Electrophilic substitutions of allyl-metal compounds

Enolate compounds allylic derivatives

Enolate compounds allylic electrophiles

Enolate compounds carbonyl allylation

Ethylamine, cyclohexylsynthesis reaction with allyl organometallic compounds

Ethylamine, phenylaldimines derived from reaction with allyl organometallic compounds

Formation of Allylic Metal Compounds

Gem-Amino ethers, N- reactions with allyl organometallic compounds

Glyoxylates reaction with allyl organometallic compounds

Heptan-2-one reaction with allylic organometallic compounds

Heterosubstituted Allylic and Benzylic Compounds

Hydride compounds allylic hydrogenolysis

Hydrogen iodide allylic compounds

Hydrogenolysis of Allylic Compounds

Hydroxylamine, V- reaction with allyl organometallic compounds

Iminium salts reactions with allyl orgnometallic compounds

Intramolecular allylation of carbonyl compounds

MO theory and allyl compounds

Macrocyclic compounds allylation

Magnesium compounds allylation reactions

Malonate compounds allylic electrophiles

Manganese compounds allyl

Metal-allylic compounds

Neodymium allyl compounds

Nickel-catalysed reactions allylic compounds

Nitrogen compounds palladium-catalyzed allylation

Nucleophilic Addition of Allylic Groups from Boron Compounds

Nucleophilic attack on allylic compounds

Nucleophilic substitution allylic compounds

ORGANOLITHIUM COMPOUNDS, addition to allyl alcohols

Of allylic compounds

Organoaluminum compounds allylic

Organocopper compounds, reactions with allyl halides

Organomagnesium rearrangements allylic compounds

Organometallic compounds allyl and propargyl/allenic

Organometallic compounds allyl complexes

Organopalladium compounds allylic acetate

Organotin compounds allyls

Organozinc compounds in Claisen rearrangement of allylic alcohols

Oxidative Addition of Allylic Compounds

Oxidative addition allylic compounds

Oximes reactions with allyl organometallic compounds

Oxotropic isomerizations of allylic compounds

Oxygen nucleophiles allylic compounds

Palladium allyl compounds

Palladium-catalysed reactions allylic compounds

Pathways to Allylic and Cyclic Compounds

Pd-Catalyzed Allylic C-Alkylation of Nitro Compounds

Phosphine ligands allylic compounds

Photochemical reduction allylic compounds

Poly allyl compounds

Polymerization allyl compounds

Polysulfones by the Reaction of Allylic Compounds with Sulfur Dioxide

Potassium compounds allylic halides

Prochiral compounds allylations

Propene allyl compounds

Propionaldehyde, 2- methoxyaldimine derivatives reaction with allyl organometallic compounds

Pyrrolidine, 3-methylenesynthesis allyl organometallic compounds

Quaternary carbon compounds allylic alkylation

Reactions of Allylic Compounds

Reactions with allyl metal compounds

Reactions with allylic organocadmium compounds

Rearrangement of Allylic Organomagnesium Compounds

Silicon compounds allylation reactions

Silylimines, N-trimethylreaction with allyl organometallic compounds

Structures of some 7r-organometallic compounds containing allyl groups as ligands

Styrene with transition metal allyl compounds

Sulfoxides, allyl p-tolyl reactions with carbonyl compounds

Sulfoxides, allylic with aromatic compounds

Sulfur nucleophiles allylic compounds

Synthesis of Biologically Active Compounds via Allylic Substitution

Tetraallyltin, carbonyl compound allylations, scandium

Tin dichloride allylic compounds

UNSATURATED ALIPHATIC COMPOUNDS Allyl alcohol

Zirconium compounds allyl derivatives

Zirconium reagents, allylic reaction with carbonyl compounds

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