AUyl alcohols

AUyl alcohol behaves like a secondary alcohol and reacts within 7 minutes. 

Hydrogenation gives aUyl alcohol [107-18-6] C H O, its isomer propanal [123-38-6] (20), or propanol, C H O [71-23-8] (21). With acidic mercuric salt catalysts, water adds to give acetol, hydroxyacetone, C2H 02 [116-09-6] (22). 

A related report has demonstrated that aldehydes can be converted into esters in the presence of allylic alcohols [83]. Dihydrocinnamaldehyde 91 and aUyl alcohol 95 undergo a cross-condensation reaction to give ester 96. The allyl alcohol 95 also serves as a hydrogen acceptor, perhaps via an isomerization/reduction sequence (Scheme 23). 

In addition to the catalysts listed in Table 2, several rhodium(I) complexes of the various diphosphines prepared by acylation of bis(2-diphenylphosphinoethyl)amine were used for the hydrogenation of unsaturated acids as well as for that of pyruvic acid, aUyl alcohol and flavin mononucleotide [59,60]. Reactions were mn in 0.1 M phosphate buffer (pH = 7.0) at 25 °C under 2.5 bar H2 pressure. Initial rates were in the range of 1.6-200 mol H2/molRh.h. 

Maruoka has found that simple alcohols can also be used in the oxy-Michael reaction [107], Using the axially chiral biaryl catalyst 67 (1 mol%) the conjugate addition of methanol, ethanol and aUyl alcohol to a, 3-unsaturated aldehydes was examined (Scheme 29). Despite moderate yields (55-83%) and enantioselectivities (16-53% ee), the high activity of this catalyst suggests that further optimisation... 

Acrolein is a metabolite of allyl alcohol and cyclophosphamide, and these compounds should be considered in acrolein metabolism schemes (Beauchamp et al. 1985 Cohen et al. 1992). AUyl alcohol in the presence of NADPH and liver or lung microsomes degrades to acrolein, acrylic acid, and glycidol (Figure 10.1). 

The epoxidation of enones using chiral phase transfer catalysis (PTC) is an emerging technology that does not use transition metal catalysts. Lygo and To described the use of anthracenylmethyl derivatives of a cinchona alkaloid that are capable of catalyzing the epoxidation of enones with remarkable levels of asymmetric control and a one pot method for oxidation of the aUyl alcohol directly into... 

When the double bond has no substituents, as in aUyl alcohol, but-3-ene-... 

Additional results of the enhancement in phenol conversion (to dihydroxy benzenes) and oxidation of aUyl alcohol (to glycidol and allyhc oxidation products) catalyzed by TS-1 in various solvents are illustrated in Fig. 46. In solvents with high dielectric constants, the heterolytic cleavage of the 0—0 bond... 

A similar conclusion was also reached by Sankar et al. (46), who used EXAFS/ DFT techniques. From the selective decrease in the EPR intensity of the A type superoxo species during the epoxidation of styrene and aUyl alcohol (Fig. 52), Srinivas et al. (52) concluded that these types of 0x0 species are preferentially consumed during the reaction. 

The main goal of recent research in this area has been to find efficient asyimnetric versions of nonradical metal-catalyzed epoxidation and hydroxylation reactions. The Sharpless epoxidation converts aUyl alcohols to the epoxides with exceptionally high e.e.s. and with predictable absolute configuration. The catalyst dictates the configuration independent of the substitution pattern. 

With suitable additives, Pd(OAc)2 can catalyze the allylation of even aldehydes using aUyl alcohol as the aUyl... 

The formal substitution of one methyl, chloro or hydroxyl group at the allylic position of propene results into the reachvity order 1-butene > allyl chloride > aUyl alcohol. Methyl substitution on butenes also produces the expected ordering 2-methyl-2-butene > 2-methyl-l-butene > 3-methyl-1-butene (Table 18.8). 

Sulfeny 1 chlondes react with aUyl alcohols to yield allyl sulfenates, which are in equihbnum with the allyl sulfoxides [12] (equation 9a) These products can be oxidized to the corresponduig sulfones (equation 9b) Pyrolysis of the sulfoxides gives sullines or evidence for the presence of sulfmes Pyrolysis of sulfones leads to unsaturated compounds by extrusion of sulfur dioxide [12] (equation 9c)... 

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