Manganese carbon-oxygen bonds

Considering the high reactivity of the active manganese (Mn ) metal prepared by the Rieke method and the exceptional tolerance to a wide range of functionality in the organic moiety, we explored the possibility of the direct oxidative addition to a variety of carbon-oxygen bonds. Our first approach employed benzyl sulfonates. This was expanded to functionalized and... 

As shown in the manganese- and ruthenium-catalyzed intermolecular nitrene insertions, most of these results supposed the transfer of a nitrene group from iminoiodanes of formula PhI=NR to substrates that contain a somewhat activated carbon-hydrogen bond (Scheme 14). Allylic or benzylic C-H bonds, C-H bonds a to oxygen, and very recently, Q spz)-Y bonds of heterocycles have been the preferred reaction sites for the above catalytic systems, whereas very few examples of the tosylamidation of unactivated C-H bonds have been reported to date. 

Mechanism The mechanism of the aliphatic side-chain oxidation as shown in Scheme 7.34 probably involves manganese-oxygen-carbon bonding with subsequent reduction of manganese and oxidation of carbon to yield aldehyde, which is much more vulnerable to oxidation with permanganate. 

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