Hydrogenolysis allylic compounds

The Pd-catalyzed hydrogenolysis of allylic compounds by various hydrides gives alkenes. From terminal allylic compounds, either 1-alkenes or 2-alkenes are formed depending on the hydride sources [360a]. 

In addition to the preparation of l-alkenes, the hydrogenolysis of allylic compounds with formate is used for the protection and deprotection of carboxylic acids, alcohols, and amines as allyl derivatives (see Section 2.9). 

Various terminal allylic compounds are converted into l-alkenes at room temperature[362]. Regioselective hydrogenolysis with formate is used for the formation of an exo-methylene group from cyclic allylic compounds by the formal anti thermodynamic isomerization of internal double bonds to the exocyclic position[380]. Selective conversion of myrtenyl formate (579) into /9-pinene is an example. The allylic sulfone 580 and the allylic nitro compound... 

Furthermore, the regioselective hydrogenolysis can be extended to internal allylic systems. In this case, clean differentiation of a tertiary carbon from a secondary carbon in an allylic system is a problem. The regioselectivity in the hydrogenolysis of unsymmetrically substituted internal allylic compounds depends on the nature and size of the substituents. The less substituted alkene 596 was obtained from 595 as the main product, but the selectivity was only... 

Reduction of vinylic and allylic compounds without hydrogenolysis may present a problem. The ratio of olefin saturation to hydrogenolysis depends importantly on catalyst, temperature, solvent, and pH. In both classes of compounds, hydrogenolysis is favored by polar solvents, acid, and elevated temperatures hydrogenation, by nonpolar solvents and low temperatures. 

A frequent problem is selective reduction of an acetylene to the olefin in the presence of other easily reducible functions. Usually the reaction can be done without difficulty because of the relatively strong and preferential adsorption of the acetylenic function on the catalyst. Functions adjacent to the triple bond may cause special problems if the resulting allylic compound is itself susceptible to facile hydrogenolysis (18,23). The product composition is, as expected, sensitive to steric effects (82). 

In some cases it is necessary to hydrogenate allylic compounds to saturated molecules without hydrogenolysis. It was found that nickel boride is a good catalyst for this purpose.46... 

Besides formic acid, many other reducing agents, such as LiAlH4, borohy-drides, hydrosilanes, and tin hydrides have been used for the hydrogenolysis of allylic compounds [7]. 

Acetylenic carbinols, which are manufactured from aldehydes or ketones and acetylenes, can be partially hydrogenated, with the exception of propargyl alcohol itself. Hydrogenolysis is a minor side reaction unless the hydrogenation is completed to the alkane. Nickel boride (PI or P2) catalysts achieve the saturation of propargyl and allylic compounds in the presence of double bonds without hydrogenolysis, such as in 2 an intermediate in the total synthesis of the sesquiterpene sesquicarene ... 

Hydrogenolysis of allylic compounds was rather general, including halides, acetates, alcohols, ethers and amines. 

Pd-catalyzed hydrogenolysis of allylic compounds with various hydride sources is important not only for the preparation of alkenes, but also for a deprotection of aUyl-derived protecting group. The latter will be discussed in Sect. V.2.3.2. 

It is well known that allylic compounds undergo facile Pd-catalyzed transformation via formation of 7r-allylpalladium complex as an intermediate, followed by attack of various nucleophiles (Scheme 1). Hydride attack on the 7r-allylpalladium intermediate affords the corresponding alkenes as hydrogenolysis products. ... 

Pd-catalyzed hydrogenolysis of allylic compounds with formates is an efficient and mild method. The most important feature of the hydrogenolysis is that the hydride generated from the palladium formate attacks the more substituted side of the allylic system to give less substituted olefins. Various terminal allylic compounds are converted to 1-alkenes. - ... 

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