Dehomologation of aldehydes has been first successfully achieved via oxidative cleavage of silyl
enol ethers, derived from aldehydes and trimethylchlorosilane, using aqueous hydrogen peroxide
in the presence of a catalytic amount of peroxotungstophophate (PCWP) under phase-transfer
conditions. For instance, the oxidation of 1-[(trimethylsilyl)oxy]-1-octene resulting from octanal
and Me3SiCl with 35% H2O2 catalyzed by PCWP in dichloromethane at room temperature afforded
the one-carbon shorter aldehyde, heptanal, in 79% yield. A variety of silyl enol ethers were also
converted into one-carbon shorter aldehydes in good yields. The oxidation under homogeneous
conditions using tert-butyl alcohol gave hydrolysis products such as 2-oxooctanol and octanal. It is
of interest that [1-(trimethylsilyl)oxy]-1,10-undecadiene involving an enol moiety and a terminal
double bond afforded exclusively 9-decenal, in which the enol moiety was selectively oxidized. A
plausible reaction path for the oxidative cleavage of silyl enol ethers by the present system has
been suggested from the oxidation results of α-[(trimethylsilyl)oxy]styrene.
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