Formate decarboxylation

Primary propargylic formates decarboxylate in the presence of Pd(acac)2 and Bu3P at room temperature to give mainly allenic products (Eq. 9.115) [91]. Initial formation of a propargylic palladium complex, which rearranges to the more stable allenylpalladium species, accounts for this transformation. Under similar conditions, a terminal allenyl formate afforded a 99 1 mixture of allene and acetylene product (Eq. 9.116) [91]. However, a mixture of enyne elimination products was formed when a secondary propargylic carbonate was treated with a palladium catalyst (Eq. 9.117). 

Decreased Benzoyl Formate Decarboxylation Activity of Variant 55E4... 

If a bis(trialkyltin) oxide (R3Sn)20 (R = Bu, Bu1, or Oct) is heated with one molar equivalent of formic acid, the formate decarboxylates to give the hydride, which reduces in situ the excess oxide to give the corresponding distannane (Section 18.2.1.3).30... 

The chemical reactivity of resin acids is determined hy the presence of hoth the double- bond system and the COOH group [5], The carboxylic group is mainly involved in esterification, salt formation, decarboxylation, nitrile and anhydrides formation, etc. These reactions are obviously relevant to both abietic- and pimaric-type acids (Rgs 4.1 and 4.3, respectively). The olefinic system can be involved in oxidation, reduction, hydrogenation and dehydrogenation reactions. Given the conjugated character of this system in the abietic-type acids, and the enhanced reactivity associated with it, much more attention has been devoted to these stractures. In terms of industrial applications, salt formation, esterification, and Diels-Alder additions are the most relevant reactions of resin acids. 

Mean Tafel Parameters for the Aqueous Formate Decarboxylation Reaction (5°C)... 

Regioselectivity of C—C double bond formation can also be achieved in the reductiv or oxidative elimination of two functional groups from adjacent carbon atoms. Well estab llshed methods in synthesis include the reductive cleavage of cyclic thionocarbonates derivec from glycols (E.J. Corey, 1968 C W. Hartmann, 1972), the reduction of epoxides with Zn/Nal or of dihalides with metals, organometallic compounds, or Nal/acetone (seep.lS6f), and the oxidative decarboxylation of 1,2-dicarboxylic acids (C.A. Grob, 1958 S. Masamune, 1966 R.A. Sheldon, 1972) or their r-butyl peresters (E.N. Cain, 1969). 

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... 

The formation of 1-and 2-aIkenes can be understood by the following mechanism. In the presence of formate anion, the 7r-allylpalladium complex 572 is converted into the 7r-allylpalladium formate 573. The most interesting feature is the attack of the hydride from formate to the more substituted side of the (T-allylic system by the cyclic mechanism shown by 574 to form the 1-alkene 575[367]. The decarboxylation and hydride transfer should be a concerted... 

The carbon-carbon bond forming potential inherent m the Claisen and Dieckmann reac tions has been extensively exploited m organic synthesis Subsequent transformations of the p keto ester products permit the synthesis of other functional groups One of these transformations converts p keto esters to ketones it is based on the fact that p keto acids (not esters ) undergo decarboxylation readily (Section 19 17) Indeed p keto acids and their corresponding carboxylate anions as well lose carbon dioxide so easily that they tend to decarboxylate under the conditions of their formation... 

Oxo 2 propylheptanoic acid (not isolated decarboxylates under conditions of its formation)... 

When both building block units are m place on the acyl carrier protein carbon-carbon bond formation occurs between the a carbon atom of the malonyl group and the carbonyl carbon of the acetyl group This is shown m step 1 of Figure 26 3 Carbon-carbon bond formation is accompanied by decarboxylation and produces a four carbon acetoacetyl (3 oxobutanoyl) group bound to acyl earner protein... 

The four carbon atoms of the butanoyl group originate m two molecules of acetyl coenzyme A Carbon dioxide assists the reaction but is not incorporated into the prod uct The same carbon dioxide that is used to convert one molecule of acetyl coenzyme A to malonyl coenzyme A is regenerated m the decarboxylation step that accompanies carbon-carbon bond formation... 

In keeping with its biogenetic origin m three molecules of acetic acid mevalonic acid has six carbon atoms The conversion of mevalonate to isopentenyl pyrophosphate involves loss of the extra carbon as carbon dioxide First the alcohol hydroxyl groups of mevalonate are converted to phosphate ester functions—they are enzymatically phosphorylated with introduction of a simple phosphate at the tertiary site and a pyrophosphate at the primary site Decarboxylation m concert with loss of the terti ary phosphate introduces a carbon-carbon double bond and gives isopentenyl pyrophos phate the fundamental building block for formation of isoprenoid natural products... 

Results obtained for two mixed plastics are summarized in Table 4. A balance exists between process temperature, plastics feed rate, and product yields (67). For example, lower temperatures increase wax formation due to incomplete depolymerization. Slower feed rates and increased residence times reduce wax formation and increase the yield of Hquids. The data summarized in Table 4 illustrate that the addition of PET to a HDPE PP PS mixture changes the performance of the Conrad process. Compared to the reference HDPE PP PS mixture, increased amounts of soHds ate formed. These are 95% terephthahc acid and 5% mono- and bis-hydroxyethyl esters. At higher temperatures, apparentiy enough water remains to promote decarboxylation. 

The principal steps in the mechanism of polyisoprene formation in plants are known and should help to improve the natural production of hydrocarbons. Mevalonic acid, a key intermediate derived from plant carbohydrate via acetylcoen2yme A, is transformed into isopentenyl pyrophosphate (IPP) via phosphorylation, dehydration, and decarboxylation (see Alkaloids). IPP then rearranges to dimethylaHyl pyrophosphate (DMAPP). DMAPP and... 

In addition to formation from a ketone, the hydra2ones can be obtained from dicarbonyl compounds by a Japp-Klingemann reaction. This is especially useful for P-ketoesters and P-ketoacids, which undergo either deacylation or decarboxylation. 

P-Peroxylactones undergo thermal decarboxylation to carbonyl compounds by the initial formation of a 1,5-diradical (238). a-Peroxylactones undergo similar decarboxylation, emitting light since the ketone is generated in the triplet excited state (85,239,240) ... 

Carboxylic Acid Group. Reactions of the carboxyl group include decarboxylation, reduction to alcohols, and the formation of salts, acyl hahdes, amides, and esters. 

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