Palladium trans

A. Farkas, On the rate determing step in the diffusion of hydrogen through palladium, Trans. Faraday Soc. 32 1667 (1936). 

S. A. Koffler.). B. Hudson, G. S. Ansell, Hydrogen permeation through alpha-palladium. Trans. Metall. Soc. AIMS 1969, 245,1735-1740. 

Other experiments have corroborated these results. It is appropriate to reiterate the results of Hayashi s study on the stereochemistry of the cychzation of the ortho-allyl phenol that was presented in Chapter 9. As shown in Scheme 16.32, the reaction with t7-ans-3-deuterio cyclohexenylphenol forms deuterated products, and the formation of these products demonstrates that the C-0 bond formation occurs by migratory insertion. As noted in Chapter 9, migratory insertion to form a cis ring juncture places the palladium trans to deuterium, and this disposition of the deuterium and the palladium leads to P-hydrogen elimination instead of p-deuterium elimination. 

It could be argued that the cyclization does not proceed by C-H activation, but by formation of an electrophilic T -complex 3.25, which is then attacked by the electron-rich indole (pathway 1). If this were the ease, a distereoisomeric t -complex 3.26, with palladium trans to the indole would be involved, whereas, by the C-H activation mechanism (pathway 2), the palladium and the indole in the intermediate 3.30 would have the cis relationship, resulting from alkene insertion. As the C-Pd bond is converted to a C-H bond, the same final product is obtained. The C-H activation mechanism of pathway 2 was demonstrated by using NaBD4 to introduce deuterium, in place of hydrogen (Scheme 3.12). The product 3.31 was found to have D cis to the indole. 

The cyclometallated palladium and platinum derivatives of trimesityl phosphine or arsine react with pyrazole or 3,5-dimethylpyrazole to form metal chelates 243 (E = P, As M = Pd, Pt R = H, Me) having the trans configuration (81TMC24). 

Dimethyl-1,2,4-triazolium iodide with palladium acetate yields the carbene adduct 182 (97JOM(530)259). Under water it undergoes cis-trans isomerization to 183. Some other derivatives were reported in 1981 (81BCSJ800). 1,1 -Methylenebis(4-alkyl-l,2,4-triazolium)diiodides (alkyl = /-Pr, n-Bu, octyl) with palladium(II) acetate give the mononuclear complexes [L Pdl ] (99EJIC1965), where L2= l,l -methylenebis(4-R-l,2,4-triazol-2-ylidene) (R = /-Pr, n-Bu, octyl). Thermolysis of the products in THF gives the rran -dinuclear complexes 184... 

In this experiment, advantage is made of the fact that lithium-ammonia reduction usually proceeds to give trans-fused Decalins 4). Thus, hydrogenation of A -octal one-2 over palladium catalyst gives essentially cw-2-decalone as the product, whereas the lithium-ammonia reduction of the octalone gives the trans ring fusion. 

Choice of catalyst and solvent allowed considerable flexibility in hydrogenation of 8. With calcium carbonate in ethanol-pyridine, the sole product was the trans isomer 9, but with barium sulfate in pure pyridine the reaction came to a virtual halt after absorption of 2 equiv of hydrogen and traws-2-[6-cyanohex-2(Z)-enyl]-3-(methoxycarbonyl)cyclopentanone (7) was obtained in 90% yield together with 10% of the dihydro compound. When palladium-on-carbon was used in ethyl acetate, a 1 1 mixture of cis and trans 9 was obtained on exhaustive hydrogenation (S6). It is noteworthy that in preparation of 7 debenzylation took precedence over double-bond saturation. 

The use of ionic liquids as reaction media for the palladium-catalyzed Heck reaction was first described by Kaufmann et ak, in 1996 [85]. Treatment of bromoben-zene with butyl acrylate to provide butyl trans-cinnamate succeeded in high yield in molten tetraallcylammonium and tetraallcylphosphonium bromide salts, without addition of phosphine ligands (Scheme 5.2-16). 

Alkynes can be reduced to yield alkenes and alkanes. Complete reduction of the triple bond over a palladium hydrogenation catalyst yields an alkane partial reduction by catalytic hydrogenation over a Lindlar catalyst yields a cis alkene. Reduction of (he alkyne with lithium in ammonia yields a trans alkene. 

In the direct coupling reaction (Scheme 30), it is presumed that a coordinatively unsaturated 14-electron palladium(o) complex such as bis(triphenylphosphine)palladium(o) serves as the catalytically active species. An oxidative addition of the organic electrophile, RX, to the palladium catalyst generates a 16-electron palladium(n) complex A, which then participates in a transmetalation with the organotin reagent (see A—>B). After facile trans- cis isomerization (see B— C), a reductive elimination releases the primary organic product D and regenerates the catalytically active palladium ) complex. 

The palladium-catalyzed cyclization of compound 138 amply demonstrates the utility of the Stille reaction as a macrocyclization method (see Scheme 37). This efficient ring closure is just one of many examples disclosed by J.E. Baldwin and his group at Oxford.58 Interestingly, compound 138 can be employed as a stereoisomeric mixture of vinylstannanes because both stereoisomers converge on the same cyclized product. To rationalize this result, it was suggested that the configuration of the vinylstannane moiety is conserved in the cyclization, but that the macrocycle resulting from the (Z)-vinylstannane stereoisomer isomerizes to the thermodynamically favored trans product under the reaction condi-... 

An intramolecular palladium(o)-catalyzed cross-coupling of an aryl iodide with a trans vinylstannane is the penultimate maneuver in the Stille-Hegedus total synthesis of (S)-zearalenone (142) (see Scheme 38).59 In the event, exposure of compound 140 to Pd(PPh3)4 catalyst on a 20% cross-linked polystyrene support in refluxing toluene brings about the desired macrocyclization, affording the 14-membered macrolide 141 in 54% yield. Acid-induced hydrolysis of the two methoxyethoxymethyl (MEM) ethers completes the total synthesis of 142. 

The exocyclic C — C double bond in the chlorin can be reduced by catalytic hydrogenation in tetrahydrofuran/water in the presence of palladium(II) acetate with triethoxysilane as hydrogen source to yield under kinetic control cw-stereoisomers, which can be transformed by treatment with /)-toluenesulfonic acid in methanol to the thermodynamically favored trans-isomers.27d... 

Hydrogenolysis of the acetylene-cumulenes 19 can be achieved by means of a partially poisoned palladium catalyst to yield the regular [22]porphyrin(2.2,2.2) 20 with cisjrans.cis,-trans configuration of the two-carbon bridges. 

Palladium(O)-catalyzed isomerization of 2-dienylaziridines 201 to 3-pyrrolines 202 was reported in 1985 by Oshima, Nozaki, and coworkers (Scheme 2.49) [78]. This isomerization is in striking contrast to Ibuka s palladium-catalyzed isomerization of 2,3-trans-2-vinylaziridines to the corresponding 2,3-cis isomers (see Section 2.4.6) [29]. 

As described in Section 2.3.2, vinylaziridines are versatile intermediates for the stereoselective synthesis of (E)-alkene dipeptide isosteres. One of the simplest methods for the synthesis of alkene isosteres such as 242 and 243 via aziridine derivatives of type 240 and 241 (Scheme 2.59) involves the use of chiral anti- and syn-amino alcohols 238 and 239, synthesizable in turn from various chiral amino aldehydes 237. However, when a chiral N-protected amino aldehyde derived from a natural ot-amino acid is treated with an organometallic reagent such as vinylmag-nesium bromide, a mixture of anti- and syn-amino alcohols 238 and 239 is always obtained. Highly stereoselective syntheses of either anti- or syn-amino alcohols 238 or 239, and hence 2,3-trans- or 2,3-as-3-alkyl-2-vinylaziridines 240 or 241, from readily available amino aldehydes 237 had thus hitherto been difficult. Ibuka and coworkers overcame this difficulty by developing an extremely useful epimerization of vinylaziridines. Palladium(0)-catalyzed reactions of 2,3-trons-2-vinylaziri-dines 240 afforded the thermodynamically more stable 2,3-cis isomers 241 predominantly over 240 (241 240 >94 6) through 7i-allylpalladium intermediates, in accordance with ab initio calculations [29]. This epimerization allowed a highly stereoselective synthesis of (E) -alkene dipeptide isosteres 243 with the desired L,L-... 

Yamamoto and coworkers developed cycloadditions between activated olefins and vinylaziridines 253 with the aid of a palladium(O) catalyst (Scheme 2.63) [94], based on their three-component aminoallylation reaction. The corresponding 4-vi-nylpyrrolidines 255 were obtained as mixtures of diastereomers (ds trans= 55 45 to 23 77). 

In 1991, Ohfune and coworkers reported palladium(O)-catalyzed carbonylation of vinylaziridines 262 with carbon monoxide (1 atm.) in benzene (Scheme 2.65) [31]. Interestingly, 3,4-trans-azetidinone 264 was exclusively obtained from a dia-stereomeric mixture of trans- and cis-vinylaziridines 262 (3 1). Tanner and Somfai synthesized (+)-PS-5 (267) by use of palladium(O)-catalyzed trons-selective (3-lactam formation in the presence of Pd(dba)3 CHC13 (15mol%) and excess PPh3 in toluene. 

Tertiary phosphine complexes of platinum and palladium M(PR3)2X2 are important [95]. The cis- and trans- somers are readily obtained for platinum,... 

DNA polymerases, 5, 1007 Trans effect, 1,16, 26, 315 metal complexes, 2, 705, palladium(II) amine complexes, 5, 1115 platinum complexes, 5, 353, 493 six-coordinate compounds. 1, 49 T ransestcrification metal alkoxide synthesis, 2, 340 Transferases zinc, S, 1002... 

Early 2005, Leadbeater s team reported that the previously claimed tran-sition-metal-free Suzuki-type protocol was definitely palladium-catalyzed [ 53 ]. Palladium contaminants down to the level of 50 ppb found in commercially available sodium carbonate were responsible for the generation of the biaryl. For good product yields in a short reaction time under microwave irradiation, a loading of 1 ppm Pd was required. 

As far as the reactions with benzyl chlorides are concerned (74), the oxidative addition of benzyl chloride and substituted benzyl chlorides to palladium atoms yields rj -benzylpalladium chloride dimers. The parent compound, bis(l,2,3-7 -benzyl)di-/i,-chloro-palladium(II), quantitatively adds four molecules of PEts by first forcing the rj -benzyl-iy -benzyl transformation, with subsequent breakage of the Pd-Cl bridges to form trans-bistPEtsKbenzyDchloroPddI). The spectral characteristics of the parent molecule are indicative of the allylic type of bonding. Similar i7 -benzyl compounds were formed from 4-methylbenzyl chloride, 2-chloro-l,l,l-trifluoro-2-phenylethane, and 3,4-dimethylbenzyl chloride. 

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