References

Main Reference:

VanRheenen, V.; Kelly, R.C.; Cha, D.Y. Tetrahedron Lett. 1976, 17, 1973.

Some of the conclusions about the mechanism that we can derive from this paper include the conditions necessary for cis-dihydroxylation. The conditions presented in the paper are: OsO₄ in a solvent of either aqueous acetone or aqueous t-BuOH (tert-butanol). Also, the paper shows that the -OH groups add cis to the alkene double bond in every case. The general mechanism steps are as follows: the alkene double bond attacks one of the oxygen atoms of OsO₄, which results in the attack of the carbon with a partially positive charge by another oxygen of OsO₄ (see overall mechanism in part (a), for picture). The oxygen atoms attached to the former alkene are protonated by water. Then, water attacks the OsO₄ twice, causing the bond to break between the oxygen atoms that were bonded to the former alkene. After this step we are left with two hydroxyl groups which added syn to the alkene. It is possible that steric hindrance could result in the preference of a certain stereoisomer.

Citing Papers:

1. Heravi, M.M.; Zadsirjan, V.; Esfandiyari, M.; Lashaki, T.B. Tetrahedron 2017, 28, 987-1043.

Sharpless Osmium Tetroxide dihydroxylation is a technique used in the presence of chiral quinine ligand to create a vicinal diol. This paper emphasizes the applications of this technique.

2. Hong, A.Y.; Vanderwal, C.D. Tetrahedron 2017, 73, 4160-4171.

This paper presents the strategy for the synthesis of the Alsmaphorazine B. One of the steps in the formation of this molecule is the formation of lagumicine from the akuammicine. In order to make lagumicime, first a dihydroxylation on akuammicine must be performed.

3. Yadav, J. S.; Dhara, S.; Mohapatra, D. K. Tetrahedron 2017, 73, 1358-1366.

In order to synthesize 10-epi-tirandamycin E, a step in which is a substrate-controlled dihydroxylation is required. This papers employs the dihydroxylation method presented in the paper by VanRheenen et. al.