Rearrangement electron-deficient oxygen

It might reasonably be expected that similar rearrangements would also occur in which the migration terminus was an electron-deficient oxygen atom such rearrangements are indeed known. 

The formation of an intermediate with electron-deficient oxygen is also one of the possible paths for the oxidation of alcohols. An intermediate such as LVI, or the chromate ester LVII which might behave in similar fashion, could rearrange to give "abnormal products or lose a proton to give the usual, expected product.889-882... 

The mechanism of the rearrangement is an excellent practical industrial example of a broad type of rearrangement, one occurring with an electron-deficient oxygen. The mechanism is given in Fig. 10.2. 

Incidentally, the oxidation step presumably involves a standard syn shift to an electron-deficient oxygen with retention at carbon. The [1,2] Stevens rearrangement also goes with retention of the migrating group (Zimmerman, 1963). 

Similar migrations to electron-deficient oxygen also occur. In the Baeyer-Villiger rearrangement a ketone is reacted with a peracid. The product is an ester in which one of the alkyl groups of the ketone has migrated to oxygen ... 

Rearrangement of hydroperoxides. Migration to electron-deficient oxygen... 

The phenyl group is joined to carbon in the hydroperoxide and to oxygen in phenol clearly, rearrangement takes place. This time, it involves a 1,2-shift to electron-deficient oxygen. 

Rearrangement to Electron-Deficient Oxygen The Baeyer-Villiger oxidation, like the Hock rearrangement, is an example of a molecular rearrangement to oxygen. Examples are shown in Equations 6.9 and 6.10. The... 

There are several analogies for this kind of rearrangement that involve electron-deficient carbon (Sections 8-9B and 15-5E) and oxygen (Sections 16-9E). 

In this chapter we shall discuss intramolecular rearrangements to electron-deficient carbon, nitrogen, and oxygen. 

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