Oxidation of secondary alcohols and ethers by dimethyldioxirane

The oxidation of several series of secondary alcohols 2-9, ethers 10-17, an d related derivatives 18 and 19, by dimethyldioxirane, 1, in acetone at 25 degrees C produced the corresponding ketones in good to excellent yields fo r all but two cases. (The exceptions: oxidation of 1-methoxy-2-methyl-1-phe nylpropane (48%) and 1-methoxy-2,2-dimethy1-1-phenylpropane (24%).) The oxi dation of the secondary alcohols was found to yield k(2) values that were r oughly 10-fold greater than those of the corresponding methyl ethers. The r ate constant for oxidation of a silyl ether was slightly lower than that fo r the corresponding methyl ether while that for the ester derivative was ro ughly half the value. For oxidation of alcohols and methyl ethers, the k(2) values became smaller as the R" series (Me, Et, nPr, iPr, and tBu) increas ed in steric bulk (rho* = 1.7; r = 0.998 and rho* = 3.2; r = 0.95, respecti vely). The Hammett study for the oxidation of the methyl ethers of ol-methy l-p-benzyl alcohols (10, 20-25) yielded a rho value of -0.74. The activatio n parameters for oxidation of the parent compound of the ether series (1-me thoxy-1-phenylethane) were Delta H-double dagger = 14.8 +/- 0.5 kcal/mol, D elta S-double dagger = -21.9 eu, Delta G(double dagger) = 21.3 kcal/mol, k( 2) (25 degrees C) = 1.6 x 10(-3) M-1 s(-1). The mechanistic aspects of the oxidation are discussed in relation to two mechanistic extremes: (a) direct insertion of the oxygen atom into the C-H bond and (b) direct abstraction of the H by dimethyldioxirane to yield a caged-radical pair, with subsequen t coupling to hemi-ketal intermediates that fragment to yield acetone, alco hol or water, and ketone as the final products.