Malaprade Glycol Oxidative Cleavage

• General Characteristics

Periodic acid or sodium periodate is used to oxidatively cleave 1,2-diols, producing a pair of aldehydes or ketones.

Sodium periodate also works as the reoxidant of osmium tetroxide, so these two reagents provide a way to oxidatively cleave alkenes under mild conditions.

Aqueous solvent systems are generally used for the solubility reason. Silica gel supported NaIO₄ is available when one needs to use nonpolar solvents.

• General References

・Malaprade, L. Bull. Soc. Chim. France 1928, 43, 683.;Compt. Rend. 1928, 186, 382.

• Reaction Mechanism

• Examples

Under the conditions consisting of OsO₄(cat.)/NaIO₄/2,6-lutidine, olefins can be cleaved easily. The addition of lutidine suppresses the formation of α-hydroxyketone byproduct.^[1] 

The synthesis of terpestacin.^[2]

The oxidative cleavage of partially protected mannitol.^[3]

• Experimental Procedure

• Experimental Tips

• References

[1] Yu, W.; Mei, Y.; Kang, Y.; Hua, Z.; Jin, Z. Org. Lett. 2004, 6, 3217. DOI: 10.1021/ol0400342
[2] Trost, B. M.; Dong, G.; Vance, J. A. J. Am. Chem. Soc. 2007, 129. 4540. DOI: 10.1021/ja070571s
[3] Schmid, C. R. ; Bryant J. D. Org. Synth. 1995, 72, 6. [PDF]

• Related Books

 

cleavage of diols, synthesis of aldehydes and ketones