The Rubottom oxidation is the chemical reaction of enolsilanes with m-chloroperoxybenzoic acid to give silyl-protected α-hydroxy ketones.[1][2][3]
Oxidation of the enolsilane (1) with m-chloroperoxybenzoic acid initially gives an epoxysilane (2). Rearrangement through a zwitterionic intermediate (3) gives the desired α-hydroxy ketone (4).
Although silyl enol ethers are the most common substrates for the Rubottom oxidation, peracids can be used to oxidize a variety of stabilized anions in addition to silyl enol ethers. Ketone and ester enolates, α-nitrile anions, α-imino anions, and silyl ketene acetals are all within the scope of the reaction. Site selective oxidation of these substrates depends on the selective deprotonation of the parent neutral compounds; selectivity is typically achieved by enforcing kinetic or thermodynamic control through the use of an irreversible (lithium diisopropylamide) or reversible (alkoxide) base for deprotonation, respectively.
Alternative oxidants include hypervalent iodine reagents such as iodobenzene diacetate, molecular oxygen, metal oxides (most notably osmium tetroxide), and N-sulfonyloxaziridines.[4]