Ji-allyl palladium

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. 

Interception of the ji-allyl palladium intermediate with soft nucleophiles such as morpholine and dimedone is attractive on the grounds of efficacy, economy, safety and scope. Deprotection of a phenol allyl ether in a synthesis of the antibiotic Vancomycin demonstrates that aryl iodides and chlorides remain intact [Scheme 4.227],429... 

The catalytic cycle of the palladium-catalyzed diacyloxylation follows the cycle depicted in Scheme 8-6 (X = RCOO, Y = R COO ). The coordination of a quinone in the Ji-allyl)palladium intermediate was demonstrated by NMR studies including T, measurements [58]. Attack by the second nucleophile results in the formation of the 1,4-addition product and a palladium(0)-benzoquinone complex. In an independent mechanistic study, it was shown that such Pd(0)-benzoquinone complexes, which are stable at neutral conditions (pH 7), react with weak acids to give hydroquinone and the palladium(II) salt of the acid [Eq.(36)] [59],... 

Di-/z-chloro-bis[(1 -ethyl-2-methyl-Ji-allyl) palladium], like most alkyl- and aryl-substituted 7r-allylchloropalladium dimers, is a yellow, crystalline, air-stable solid, which is soluble in organic solvents of medium polarity (acetone, dichloromethane, chloroform, benzene). The reactions of these compounds have been described in several reviews.17... 

Cationic palladium-catalyzed addition of arylboronic acids to nitriles for the formation of benzo[h]furans was reported <06OL5987>, an example of which is illustrated in the following scheme. The palladium-catalyzed cross coupling of alkynes with appropriately substituted aryl iodides for the synthesis of substituted dibenzofurans in moderate to excellent yields was also achieved <06JOC5341>. The benzo[fc]furan core of heliannuls G and H were constructed by a palladium-catalyzed Ji-allyl cyclization reaction <06TL7353>. The palladium-catalyzed oxidative activation of arylcyclopropanes was applied to the synthesis of 2-substituted benzo[Z>]furans <06OL5829>. 

The generally accepted mechanism of palladium-catalyzed allylic substitutions is shown in Scheme 1. An allylic substrate 1, typically an acetate or a carbonate, reacts with the catalyst, which enters the catalytic cycle at the Pd(0) oxidation level. Both Pd(0) and Pd(II) complexes can be used as precatalysts, because Pd(II) is easily reduced in situ to the active Pd(0) form. Presumably, the reaction is initiated by formation of a Ji-complex which eliminates X to produce an (ri -allyl)palladium(II) complex. The product of this oxidative addition can... 

Trost and coworkers have devised a stereocontrolled 1,3-diene synthesis employing a palladium-catalysed decarboxylative elimination procedure from allylic acetates carrying carboxylic acid functionality ji- to the acetate group (equation 18)48. This decarboxylative elimination strategy has been applied to the synthesis of an insect pheromone, codlemone48a and the ethyl ester of vitamin A carboxylic acid (Table 5)48b. 

As shown in Scheme 5.1, formic acid behaves differently to other carboxylic acids. Expected octadienyl formate is not formed. The reaction with formic acid in the presence of EtjN affords 1,7-octadiene (140) [62 64], The first step is the protonation of bis-Ji-allylpalladium 68 with formic acid to generate 167. Formic acid is a hydride source, ft is known that the Pd hydride, formed by the decarboxylation of palladium formate, attacks the substituted side of 7i-allylpalladium as shown by 167 to form the terminal alkene 140 [65], The regioselective attack of Pd—H at the more substituted side of 7r-allyl systems is covered in Section 4.3.7. 

A clever variation on the reactions of allylic acetates is the palladium-catalysed reaction of monoepoxides of dienes with nucleophiles. These monoepoxides can be made in two chief ways. If the diene is symmetrical 264, epoxidation of one of the alkenes occurs more rapidly than the epoxidation of the monoepoxide because the HOMO ( /2) of the diene is higher in energy and therefore more nucleophilic than the HOMO (ji) of an alkene. It is simply necessary to buffer the epoxidation reagent as these monoepoxides 265 are sensitive to acid (chapter 17). 

Synthesis of neutral Ji-allylpalladium complexes having bisnitrogen ligands (mainly, those related to 2-(pyrazol-3-yl)pyridine, 2-(imidazol-2-yl)pyridine, and 2,2-bipyridine) and palladium-catalyzed cyclopropanation of ketene silyl acetals with allylic acetates 00YGK736. 

Palladium-catalyzed substitutions of allylic esters 93, which proceed via intermediate ji-allylpalladium complexes such as 94, are well established [178]. In contrast, the reactions proceeding through 7r-allylpalladium intermediates, generated by addition of the palladium intermediates from haloarenes, haloalkenes, or the corresponding triflates, to allene and substituted allenes 95 (Scheme 3-26), have scarcely been tapped [79]. 

Gabriele et al. reported a sequential homobimetallic palladium-catalyzed cascade reaction for the synthesis of benzofuran derivatives 207 [80] (Scheme 6.57). Sequential homobimetallic catalysis is different in catalytic cycles promoted by the same metal but in different oxidation states. After oxidative addition and oxopalladation, 5-exo-dig cyclization occurs, followed by carbonylation, affording the intermediate 206. The allylic alcohol is reduced by H—Pd—I through formation of a ji-aUyl complex and the elimination of water. Finally, the product observed is afforded... 

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