Allylnickelation

TT-Allylpalladium chloride (36) reacts with the nucleophiles, generating Pd(0). whereas tr-allylnickel chloride (37) and allylmagnesium bromide (38) reacts with electrophiles (carbonyl), generating Ni(II) and Mg(II). Therefore, it is understandable that the Grignard reaction cannot be carried out with a catalytic amount of Mg, whereas the catalytic reaction is possible with the regeneration of an active Pd(0) catalyst, Pd is a noble metal and Pd(0) is more stable than Pd(II). The carbon-metal bonds of some transition metals such as Ni and Co react with nucleophiles and their reactions can be carried out catalytic ally, but not always. In this respect, Pd is very unique. 

It was also shown that a cahonic allylnickel complex [(q3-crotyl)Ni P(OEt)3 2]PF6 catalyzes this reaction without added acid and that ds- and trans-1,3-pentadienes react with morpholine to give a mixture of 1,2- and 1,4-addition products [178]. 

Nickel(O) complexes are extremely effective for the dimerization and oligomerization of conjugated dienes [8,9]. Two molecules of 1,3-butadiene readily undergo oxidative cyclization with a Ni(0) metal to form bis-allylnickel species. Palladium(O) complexes also form bis-allylpalladium species of structural similarity (Scheme 2). The bis-allylpalladium complexes show amphiphilic reactivity and serve as an allyl cation equivalent in the presence of appropriate nucleophiles, and also serve as an allyl anion equivalent in the presence of appropriate electrophiles. Characteristically, the bis-allylnickel species is known to date only as a nucleophile toward carbonyl compounds (Eq. 1) [10,11],... 

Scheme 3 Catalytic cycle for the formation of trienyl alcohols 1 via bis-allylnickel(II) intermediates 2 and 5...

The homoallylation product 16a presumably stems from oxidative cycloaddition of a Ni(0) species across the diene and aldehyde moieties of 15, leading to an oxanickellacycle intermediate 17 (path A, Scheme 5), which undergoes 0-bond metathesis with triethylsilane giving rise to a o-allylnickel 19. On the other hand, formation of 16b may start with addition of a Ni - H species upon the diene followed by intramolecular nucleophilic allylation as described in Eqs. 4-6 (path B). Alternatively, allylic transposition of the NiH group providing 20 from 19 may be related to the formation of 16b. The different reactivity between cyclohexadiene and many other acyclic dienes is also observed for the reaction undertaken under typical homoallylation conditions (see Scheme 14). 

The possible reaction pathways for the stereoselective E- and Z-allylation are illustrated in Scheme 7. 1-Silyl-l,3-dienes 22 react with a Ni-H species in the presence of PPI13 to provide a syn-it-allylnickel species 24, the least substituted allylnickel species, which undergoes nucleophilic addition to an aldehyde at the least substituted allylic terminus to provide ( )-allylsilanc ( )-23. It should be noted that the regioselectivities observed for the Ni-H addition to a diene 22 and nucleophilic addition of 24 to aldehydes are opposite to those observed so far in many precedents in this review (e.g., Eqs. 4 and 6). 

A combination of organometallic procedures has been used in the design of a simple, efficient synthesis of 2-alkylindoles from o-bromoanilines.76 The arylamines are converted in reactions with 73-allylnickel dimers77 into 2-allylarylamines (36, Scheme 48) which can be cyclized in a separate step... 

The behavior of 3 toward ether or amines on the one hand and toward phosphines, carbon monoxide, and COD on the other (Scheme 2), can be qualitatively explained on the basis of the HSAB concept4 (58). The decomposition of 3 by ethers or amines is then seen as the displacement of the halide anion as a weak hard base from its acid-base complex (3). On the other hand, CO, PR3, and olefins are soft bases and do not decompose (3) instead, complexation to the nickel atom occurs. The behavior of complexes 3 and 4 toward different kinds of electron donors explains in part why they are highly active as catalysts for the oligomerization of olefins in contrast to the dimeric ir-allylnickel halides (1) which show low catalytic activity. One of the functions of the Lewis acid is to remove charge from the nickel, thereby increasing the affinity of the nickel atom for soft donors such as CO, PR3, etc., and for substrate olefin molecules. A second possibility, an increase in reactivity of the nickel-carbon and nickel-hydrogen bonds toward complexed olefins, has as yet found no direct experimental support. 

Examples of w-allylnickel-X compounds (X = anionic ligand) other than 77-allylnickel halides which have been used in combination with (alkyl)aluminum halides as olefin oligomerization catalysts are 7r-allyl-nickel acetylacetonate (11) (Section III), 7r-allylnickel aziridide (4, 56), and bis(7r-allyl)nickel (6) (59). In addition to ir-allylnickel halides, organo-nickel halides such as tritylnickel chloride (60, 61) and pentafluoro-phenylbis(triphenylphosphine)nickel bromide (62), or hydridonickel halides, e.g., trans-hydridobis(triisopropylphosphine)nickel chloride (12) (Section III), give active catalysts after activation with aluminum halides... 

Method B2 A modification of method B4 for the preparation of catalysts starting from organonickel halides consists in the exchange of the halide anion by an anion of a strong complex acid, HY. This has been accomplished by reacting 7r-allylnickel halides (1) or their phosphine adducts (2) with silver salts (65) ... 

An obvious method to investigate the formation and the nature of the catalytically active nickel species is to study the nature of products formed in the reaction of complexes such as 3 or 4 with substrate olefins. This has been investigated in some detail in the case of the catalytic dimerization of cyclooctene to 1-cyclooctylcyclooctene (17) and dicy-clooctylidene (18) [Eq. (4)] using as catalyst 7r-allylnickel acetylacetonate (11) or 7r-allylnickel bromide (1) activated by ethylaluminum sesquihalide or aluminum bromide (4). In a typical experiment, 11 in chlorobenzene was activated with excess ethylaluminum sesquichloride cyclooctene was then added at 0°C and the catalytic reaction followed by removing... 

The following conclusions can be drawn (a) ir-Allylnickel compounds are probably not involved in the catalytic dimerization of cyclooctene, because the highest reaction rate occurs when only traces of these compounds can be detected further, the concentration of the new 7r-allyl-nickel compound (19) becomes significant only after the catalytic reaction has ceased, (b) The complex formed between the original 7r-allylnickel compound (11) and the Lewis acid is transformed immediately upon addition of cyclooctene to the catalytically active nickel complex or complexes. In contrast to 7r-allylnickel compounds, this species decomposes to give metallic nickel on treatment of the catalyst solution with ammonia, (c) The transformation of the catalytically active nickel complex to the more stable 7r-allylnickel complex occurs parallel with the catalytic dimerization reaction. This process is obviously of importance in stabilizing the catalyst system in the absence of reactive olefins. In... 

The reversal of the insertion reaction [Eq. (10)] is not normally observed [in contrast to nickel hydride addition to olefins, Eq. (9)]. An exception is the skeletal isomerization of 1,4-dienes (88, 89). A side reaction—the allylhydrogen transfer reaction [Eq. (5)]—which results in the formation of allylnickel species such as 19 as well as alkanes should also be mentioned. This reaction accounts for the formation of small amounts of alkanes and dienes during the olefin oligomerization reactions (51). 

The reaction of ethylene at -20°C and 1 atm with the phosphine-free catalyst prepared from 77-allylnickel chloride and ethylaluminum dichloride in chlorobenzene results in the rapid formation of a mixture of ethylene dimers with lesser amounts of higher oligomers. The dimer fraction consists mainly of 2-butenes and the trimer fraction of 3-methylpentenes and 2-ethyl-1-butene as well as a minor amount of hexene (97). From the composition of the products it can be concluded that the displacement reaction predominates over the insertion reaction when using the phosphine-free catalyst and that the direction of addition of both the H—Ni and C2H5—Ni species is mainly of the Ni — C2 type. 

Acrylonitrile or methyl acrylate readily inserts into allylnickel bonds (example 34, Table HI). A trans double bond is formed by loss of a proton. Insertion of acetylene followed by oxidative elimination with allyl halides gives cis double bonds (example 32, Table III). Insertion of methyl propiolate, followed by proton uptake, leads to a trans double bond (example 33, Table III). Norbomene has been shown to insert stereoselectively cis.exo into an allylnickel bond (example 35, Table III). 

Some related reactions are worth mentioning in this context. Addition of allylnickel bromide to styrene oxide to give an alcohol has been reported (example 7, Table IV). Tsutsumi has described the Darzens-type reaction of two molecules of a-bromoketones to give dimethylfurans (example 8, Table IV). This reaction consists of the addition of the ketomethylenic group to the carbonyl group of another molecule, followed by epoxide formation and bromide elimination. A subsequent rearrangement leads to a dialkylfuran. 

Allylnickel halides also react with quinones (example 5, Table IV). 

It has been known that 7r-allylnickel halides are catalysts for polymerization of butadiene (50, 51). When the halide is chloride, the polymer formed is cis-polybutadiene when the halide is iodide, the polymer is trans-polybutadiene. Porri and co-workers (50) interpret this effect in terms of the ease of dissociation of the dimeric complex 29 by butadiene. The chloride complex... 

In the polymerization of butadiene, Teyssie (52-54) has shown that certain electron donors, such as alcohols or phosphines, can convert tt-allylnickel chloride from a catalyst which forms c/j-polybutadiene to one which produces frans-polybutadiene. These ligands presumably block a site on the nickel atom, forcing the butadiene to coordinate by only one double bond. While alcohols cannot be added directly to the hexadiene catalyst (as they deactivate the alkylaluminum cocatalysts), incorporation of the oxygen atom on the cocatalyst places it in an ideal position to coordinate with the nickel. The observed rate reduction (52) when the cri-polybutadiene catalyst is converted into a fra/w-polybutadiene catalyst is also consistent with the observed results in the 1,4-hexadiene synthesis. 

The ionization of 7r-allylnickel chloride by AlBr3 during the polymerization of butadiene has also been suggested (50, 56) as the reason for increasing the reaction rate. 

Electrochemical formation of allylnickel species and their addition to aldehydes were reported. a Allylnickel(i) species generated via one-electron reduction of 3-allylnickel(ii) intermediates are considered as active nucleophilic species. 

The reaction of CO2 with 1,3-butadienes in the presence of Ni catalysts usually gave an isomeric mixture of carboxylic acids 89 and 90 after hydrolysis (Scheme 32).47,48 The oxa-7r-allylnickel complexes 87 and 88 might be the reaction intermediates, which could be formed through oxidative cyclization of Ni(0) with C02 and the dienes. When Me2Zn was used as a transmetallation agent to react with the oxa-7r-allylnickel intermediates under a C02 atmosphere, further carboxylation took place at the 7r-allylnickel unit. Thus, the 1,4-diesters 95 were obtained after acidic hydrolysis and treatment with diazomethane as shown in Scheme 32.47... 

In the case of 1,3-cyclohexadiene with Me2Zn, the dicarboxylation afforded the /rdicarboxylic acid 96 (Scheme 33). In contrast, when Ph2Zn was used instead of Me2Zn as a transmetallation agent, the phenylative carboxylation occurred in high regio- and stereoselectivity to give the l,4-m-substituted-2-cyclohexene 97, as a result of reductive elimination from the phenyl-7r-allylnickel intermediate, prior to the second carboxylation reaction (Scheme 33).47... 

It is proposed that the reaction proceeds through (i) oxidative addition of a silylstannane to Ni(0) generating (silyl)(stannyl)nickel(n) complex 25, (ii) insertion of 1,3-diene into the nickel-tin bond of 25 giving 7r-allylnickel intermediate 26, (iii) inter- or intramolecular allylation of aldehydic carbonyl group forming alkoxy(silyl)nickel intermediate 27, and (iv) reductive elimination releasing the coupling product (Scheme 69). 

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