Allenes palladium

The palladium(II)-catalyzed oxidation of allenes with chloride was studied by Hege-dus et al. [3], In this reaction the dimeric products 4 and 6 as shown in Scheme 17.4 were obtained. The (allene)palladium(II) complex formed can react with chloride ions in two different ways (Scheme 17.4) [4]. Attack at the terminal carbon gives a vinylpalladium intermediate 2 whereas attack at the middle carbon produces a 2-chloro(jt-allyl)palladium complex 3. The former complex is the kinetic intermediate (k2 > kj) and is in equilibrium with the (allene)palladium complex. The 2-chloro(jt-allyl)palladium complex is formed more slowly but is more stable and has been isolated [2]. The vinyl complex can undergo further reaction with excess allene to give a new (jt-allyl)palladium complex, which undergoes attack with chloride to give the observed dimer 6 [3]. The dichloride from attack on the 2-chloro-(jT-allyl)palladium complex 3 was not observed. 

The propargylic palladium compound is in equilibrium with an allenic palladium compound. 

The formation of compound 175 could be rationalized in terms of an unprecedented domino allene amidation/intramolecular Heck-type reaction. Compound 176 must be the nonisolable intermediate. A likely mechanism for 176 should involve a (ji-allyl)palladium intermediate. The allene-palladium complex 177 is formed initially and suffers a nucleophilic attack by the bromide to produce a cr-allylpalladium intermediate, which rapidly equilibrates to the corresponding (ji-allyl)palladium intermediate 178. Then, an intramolecular amidation reaction on the (ji-allyl)palladium complex must account for intermediate 176 formation. Compound 176 evolves to tricycle 175 via a Heck-type-coupling reaction. The alkenylpalladium intermediate 179, generated in the 7-exo-dig cyclization of bro-moenyne 176, was trapped by the bromide anion to yield the fused tricycle 175 (Scheme 62). Thus, the same catalytic system is able to promote two different, but sequential catalytic cycles. 

AUenynes. An attractive route to allenynes involves the reaction of allcnic bromides with 1-alkynes in the presence of catalytic amounts of this Pd(0) complex and Cul in diethylamine at 25° (equation 1). The synthesis presumably involves cross-coupling between an allenic palladium cr-compound and a copper acetylide. 

Similar complexes are formed in the reaction of allylpalladium acetylacetonate (acac) and allene Palladium acetate, however, leads to a binuclear complex containing a trimer of allene ... 

C-C Bond Formation with the Use of an Allene Palladium-catalyzed aUenyl-substituted conjugated dienes 123 with the use of palladium acetate as the catalyst and BQ as the oxidant afforded products 124 by a carbocylization (Eq. (11.53)) [52]. 

Craft and Gung developed a paUadium-catalyzed transannular [4+3] cycloaddition route in which all of the rings of cortistatins are prepared in one step from a single macrocyclic precursor (Scheme 19.50) [114]. Exposure of macrocyclic allene 233 to a catalytic amount of palladium (II) acetate in the presence of excess lithium bromide resulted in the formation of 238 as a single isomer in 37% yield. This is the first report of a transannular [4+3] cycloaddition. The proposed mechanism is shown in Scheme 19.50. The formation of allene-palladium complex 234 affords a a-allylpalladium intermediate, which rapidly isomerizes to the 7i-allylpalladium intermediate 235. This can then undergo intramolecular cycloaddilion via an endo (compact) transition strucmre 236 to give bromonium ion 237. The loss of a proton results in the formation of the observed product 238. Cycloadduct 238 was readily converted into the tetracyclic core skeleton of cortistatins 239 by selective reduction of the olefin formed by cycloaddition with furan, followed by reductive debromination. 

Allenes also react with aryl and alkenyl halides, or triflates, and the 7r-allyl-palladium intermediates are trapped with carbon nucleophiles. The formation of 283 with malonate is an example[186]. The steroid skeleton 287 has been constructed by two-step reactions of allene with the enol trillate 284, followed by trapping with 2-methyl-l,3-cyclopentanedione (285) to give 286[187]. The inter- and intramolecular reactions of dimethyl 2,3-butenylmalonate (288) with iodobenzene afford the 3-cyclopentenedicarboxylate 289 as a main product) 188]. 

Selectivity depends importantly on the catalytic metal. A number of selectivity series have been determined for simple olefins, and the presumption is that the sequence holds for more complex polyenes as well. Selectivity for the reduction of allene to propylene declined with metal in the order palladium... 

Scheme 2.20 Palladium(0)-catalyzed aziridination of a-amino allene 66.

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. 

The groups R2N and Cl can be added directly to alkenes, allenes, conjugated dienes, and alkynes, by treatment with dialkyl-V-chloroamines and acids. " These are free-radical additions, with initial attack by the R2NH- radical ion. " N-Halo amides (RCONHX) add RCONH and X to double bonds under the influence of UV light or chromous chloride. " Amines add to allenes in the presence of a palladium catalyst. ... 

Sequential hydrostannation-palladium catalysed cyclisation of the allene 56 leads to formation of the vinyltetrahydobenzoxazepine 57 <96T13441>. 

The hydroamination of allene with morpholine or allylamines has been attempted with palladium-based catalysts. Usually, a mixture of 1 1 telomers (hydroamination products) and 1 2 telomers is obtained, the latter being the major [308, 309] or only... 

From the beginning of the 1970s unhl the mid 1980s, several examples of the telomerization of dienes with water [76, 77] or methanol [78, 79] to isomeric mixtures of dienols or dienol ethers catalyzed by palladium-phosphine complexes in the presence of carbon dioxide have been reported. Neither the yield nor the selectivity were very high. However, when allene was employed as a diene , 3-methyl-2-meth-ylene-3-buten-l-ol was obtained with fairly good selectivity (up to 98%) (Eq. 6.43) [78]. 

In 1996, Ogawa et al. reported the hydrothiolahon of an allene catalyzed by Pd(OAc)2 to provide 32, whose formahon can be explained as follows (1) insertion of the allene into the Pd-S bond of Pd(SPh)2 to give a tt-allyl palladium thiolate 33, and (2) protolysis by PhSH to form 32 and Pd(SPh)2 (Eq. 7.24) [35], The authors proposed the direct reachon of a o-aHyl palladium with PhSH before the formation of 33. 

A possible reaction mechanism shown in Scheme 7-10 includes (a) oxidative addition of the S-H bond to Pd(0), (b) insertion of the allene into the Pd-H bond to form the tt-allyl palladium 38, (c) reductive elimination of allyl sulfide, (d) oxidative addition of the I-aryl bond into the Pd(0), (e) insertion of CO into the Pd-C bond, (f) insertion of the tethered C=C into the Pd-C(O) bond, and (g) P-elimination to form 37 followed by the formation of [baseHjI and Pd(0). 

Me3SiPdSnBu3 is formed primarily from 6/1-237, which then adds to the allene moiety in 6/1-236 to give a a- or Jt-allyl palladium complex. This undergoes an intramolecular carbonyl allyl addition to afford the cis-cycloalkariols 6/1-238 (Scheme 6/1.61). 

As described in the preceding sections, many domino reactions start with the formation of vinyl palladium species, these being formed by an oxidative addition of vinylic halides or triflates to Pd°. On the other hand, such an intermediate can also be obtained from the addition of a nucleophile to a divalent palladium-coordinated allene. Usually, some oxidant must be added to regenerate Pd11 from Pd° in order to achieve a catalytic cycle. Lu and coworkers [182] have used a protonolysis reaction of the formed carbon-palladium bond in the presence of excess halide ions to regenerate Pd2+ species. Thus, reaction of 6/1-386 and acrolein in the presence of Pd2+ and LiBr gave mainly 6/1-388. In some reactions 6/1-389 was formed as a side product (Scheme 6/1.98). 

Diazomethane in the presence of palladium acetate gave with allenes 613 a similar mixture of methylenecyclopropanes 614 and spiropentanes 615. In contrast to Simmons-Smith reagent, diazomethane prefers to add to the less substituted allenic double bond (Scheme 87) [162]. 

Air-stable palladium(O) catalyst, [(Cy3P)2Pd(H)(H20)]BF4, catalyses carbonylation of propargylic alcohols to generate dienoic acids and esters (equation 167)286. Since propar-gyl alcohols are obtained from carbonyl compounds by acetyhde addition reactions, this sequence constitutes a three-carbon homologation. a-Allenic alcohols are converted to tt-vinylacrylic acids under similar conditions (equation 168)287. 

Attempts to employ allenes in palladium-catalyzed oxidations have so far given dimeric products via jr al lyI complexes of type 7i62.63. The fact that only very little 1,2-addition product is formed via nucleophilic attack on jral ly I complex 69 indicates that the kinetic chloropalladation intermediate is 70. Although formation of 70 is reversible, it is trapped by the excess of allene present in the catalytic reaction to give dimeric products. The only reported example of a selective intermolecular 1,2-addition to allenes is the carbonylation given in equation 31, which is a stoichiometric oxidation64. 

An example of an intramolecular palladium-catalyzed oxidation of an allene involving carbonylation was used in the synthesis of pumilotoxin 251 D (equation 32)65. Intramolecular aminopalladation of the allene followed by carbonylation of the palladium-carbon bond and subsequent oxidative cleavage of the acylpalladium intermediate by CuCE afforded pyrrolidine 72 in which the chirality at the carbon at the 2-position was established. 

Vinyl- or arylboronic acids also react with allenes, affording 1,3-dienes or styrene derivatives, respectively.89 This palladium-catalyzed addition proceeds with good regioselectivity and high stereoselectivity in favor of the formation of (ft)-trisubstituted isomer. 

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