Aryl methylthiomethyl ethers

HgCl2, CH3CN-H2O, reflux, 10 h, 90-95% yield. Aryl methylthiomethyl ethers are stable to the conditions used to hydrolyze primary alkyl MTM ethers (e.g., HgCl2/CH3CN-H20, 25°, 6 h). They are moderately stable to acidic conditions (95% recovered from HOAC/THF-H2O, 25°, 4 h). 

Cleavage of methyl ethers. Alkyl methyl ethers are converted into acetates in high yield on contact with these two reagents. Both alkyl and aryl methylthiomethyl ethers are cleaved in 60-70% yield by this system. Tertiary alcohols can be acetylated by this reaction (two examples, 90% yield)... 

The or//io-palladation of 3,4-dioxygenated benzylic tertiary amines by lithium tetrachloropalladate can be directed exclusively to either C-2 or C-6. Substitution at C-6 prevails when AcO, methylenedioxy, PhCH20, methoxymethyl ether, or HO substituents are attached to C-3, whereas palladation occurs exclusively at C-2 when C-3 bears methylthiomethyl ether or phenylthiomethyl ether substituents. The resulting organopalladium compounds are crystalline solids, stable to air and moisture, and can readily be carbonylated, alkylated, arylated, Kinetic studies of the acetoxylation of arenes by potassium peroxydisulphate and acetic acid in the presence of (2,2 -bipyridyl)palladium(ii) acetate catalyst have led to a revision of the mechanism. The reaction is now thought to proceed via... 

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