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8.1.6.3 Oxidative Cleavage of Terminal Diols to Dehomologated Carboxylic Acids

DOI: 10.1055/sos-SD-225-00271

Dornan, L. M.; Hughes, N. L.; Muldoon, M. J.Science of Synthesis: Catalytic Oxidation in Organic Synthesis, (20171557.

2,2,6,6-Tetramethylpiperidin-1-oxyl (TEMPO, 5) and 1-methyl-2-azaadamantan-N-oxyl (1-Me-AZADO, 1) can be employed for oxidative cleavage of terminal 1,2-diols to form carboxylic acids with one fewer carbon atom.[‌55‌] Using the conditions shown in Table 7, it is possible to oxidize diols 34 containing alkene, alkyne, acetonide, and N-tert-butoxycarbonyl functional groups. An additional benefit is the possibility to carry out the transformation without epimerization of adjacent stereocenters. The method is also applicable in the oxidation of terminal triols and tetraols; however, it is not possible to oxidize internal diols, and substrates bearing trisubstituted alkenes are not suitable. For some simple diols, there is little difference between the performance of TEMPO and 1-Me-AZADO; however, for a number of substrates, 1-Me-AZADO is greatly superior. This method has since been used in a multistep synthesis of irciniastatin A.[‌56‌]

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