Allyl alcohol ions, decomposition

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A mechanistic study of the role of the lanthanide cations suggests that they catalyze decomposition of borohydride by the hydroxylic solvent to afford alkoxyborohydrides, which may responsible for the observed regioselectivity. The stereoselectivity of the process is also modified by the presence of Ln " ions, in that axial attack of cyclohexenone systems is enhanced. a,p-Unsaturated aldehydes are regio-selectively reduced to allylic alcohols by bis(triphenylphosphine)copper(I) tetrahydroborate in the presence of Lewis acid catalyst. ... 

Treatment of A-nitroso-iV-(cr5-2-phenylcyclopropyl)urea with excess sodium formate in methanol at 25 "C for 15 hours affords ( )-3-methoxy-l-phenylprop-l-ene (25%) and 3-methoxy-3-phenylprop-l-ene (60%, Table 15, entry 7). An almost identical result is obtained when the tran -isomer is used as substrate. Formation of the 2-phenylcyclopropyldiazonium ion, decomposition with loss of nitrogen to the 2-phenylcyclopropyl cation, followed by ring opening to form the phenylallyl cation, can explain the result. When [l- Hi]aminocyclopropane is subjected to deamination with nitrous acid in water at 0°C (Table 15, entry 8), allyl alcohol is obtained, which is isolated as the 4-(phenylazo)benzoate derivative in 44% yield. In this case, the deuterium is only located at the C2 allyl position. ... 

This is proved by the observation that the rate of decomposition of persulphate drops to the same low value as when allyl acetate is added in the absence of alcohol. On addition of allyl acetate, the sulphate ion radicals react with the allyl monomer rather than with the alcohol, so that no alcohol radicals are formed and reaction (VII) cannot take place. Formaldehyde is only formed in the absence of allyl acetate. It should be noted that Bartlett and Nozaki (24) could not confirm these observations. 

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