Modified Kornblum oxidation

The first total synthesis of the clerodane alkaloid solidago alcohol was achieved in the laboratory of H.-S. Liu, using a highly diastereoselective DIels-Alder cycloaddition as the key step. The installation of the 3-furyl side chain required the conversion of the bicyclic primary alkyl bromide to the corresponding aldehyde. This was accomplished by the modified Kornblum oxidation, which employed silver tetrafluoroborate to activate the substrate. 

The traditional oxidation of benzylic and other halides to the aldehyde using DMSO (Kornblum oxidation) has been known for about 35 vears246,362,363. Modified oxidations of this type using selenoxides364,365 and 2-nitropropane366,367 have proved more versatile since other functional groups that are sensitive to the traditional oxidation procedure may be tolerated. In the reaction with 2-nitropropane, allylic halides are readily converted into aldehydes with retention of the alkene geometry. 

Novel fluorescent ATP analogues where the two tertiary carbons of the etheno-moiety of A A -etheno adenosine have been modified by the introduction of a /7-nitro or a / -amino-phenyl group and a hydroxy moiety (100) have been prepared via a Kornblum oxidation reaction and imidazole formation. These compounds exhibited relative stability towards type II ATPDase. ... 

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See also in sourсe #XX -- [ ]

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