10/21/2017 IfAS : India's No - 1 Life Science & Chemical Science (NET , GATE , M.Sc.

, SET) Institute

Dihydroxylation of C = C Bond
INTRODUCTION
The dihydroxylation of alkenes provides 1,2-diol products, present in a great many natural products and biologically
active molecules.
The transformation has, therefore, received considerable interest and methods are now well developed for catalytic,
racemic and asymmetric dihydroxylation.
The most common of these is syn (or cis) dihydroxylation, in which the two hydroxy groups are added to the same side
of the double bond.
The best methods involve reaction with osmium tetroxide; other reagents include potassium permanganate or iodine
with silver carboxylates.
To prepare the anti (or trans) diol product, ring-opening of epoxides is most convenient, although the Pr´evost reaction
(iodine and silver acetate under anhydrous conditions) is also useful.
The alkene may, of course, have either the E- or Z-configuration and syn dihydroxylation gives rise to isomeric diols
Treatment of alkenes either with osmium tetroxide or with alkaline potassium perrnanganate results in syn-
dihydroxylation of the double bond.

1.1) Dihydroxylation of Olefins with OsO4

The dihydroxylation of olefins with OsO4 provides a reliable method for the preparation of cis-1,2-diols.
Although osmium tetroxide is expensive, it is the reagent of choice for syn-dihydroxylation because yields of diols
obtained are usually high.
The reaction can be depicted as a concerted syn-addition of the reagent to the double bond, forming the cyclic osmate
ester, which upon hydrolysis or reduction (H2S, Na2HSO3, or Na2O3) produces the cis- 1,2-diol.

1.2) Dihydroxylation of Cis Olefins

The reaction is stereospecific in that Z-alkenes give the anti-1,2-diols.

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i.e. Meso, Erythreo,(R,S/S,R) compound.

1.3) Dihydroxylation of Trans olefins
where as (E)-alkenes furnish the syn-1,2-diols

i.e. Recimic, Threo, DL, (R,R/S,S) Compound

1.4) In a cyclic ring system Dihydroxylation
In a cyclic ring system Dihydroxylation always cis and always prefers from less hindered site

Osmium-tetroxide-catalyzed dihydroxylation of sterically hindered olefins proceeds more e iciently with

trimethylamine N-oxide in the presence of pyridine.
The base appears to catalyze not only formation of the osmate ester, but also its hydrolysis.

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1.5) Selectivity if more than one double bond

Under controlled conditions, the osmium-tetroxide-mediated dihydroxylation is also chemoselective, reacting
preferentially with the more nucleophilic double bond in the presence of a triple bond.

1.6) Dihydroxyltion by Chelation control

In contrast, dihydroxylation of allylic alcohols using stoichiometric osmium tetroxide in the presence of
tetramethylethylene diamine (TMEDA) as a ligand provides predominantly the syn product.
The diamine TMEDA coordinates to the osmium atom of OsO4, thereby increasing the electronegativity of the oxo
ligands and favouring hydrogen bonding to the allylic hydroxy group.

1.7) Dihydroxyltion by epoxide opening

Payne rearrangement by treatment of 2,3-epoxy alcohol A with aqueous NaOH in the presence of a cosolvent to form a
anti dihydroxy compound.

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1.8) Combine Dihydroxylation

Epoxidation of olefins followed by ring opening with OH- provides 1,2 diols with Trans stereochemistry from that
observed with osmiumtetroxide- mediated reaction syn-dihydroxylation.

1.9) Potassium Permanganate

The reaction of alkenes with alkaline potassium permanganate proceeds rapidly via formation of a cyclic manganese
ester, which is hydrolyzed to the 1,2-diol.
To avoid overoxidation to an acyloin (a-ketol), the pH of the reaction medium has to be monitored.
Although the yields of cis-diols obtained are usually modest (-50%), the procedure is less hazardous and much less
expensive than using osmium tetroxide and thus is well suited for large-scale preparations.
Improved yields of diols are obtained when the oxidation is carried out in water in the presence of a phase transfer
agent such as benzyltriethylammonium chloride.

1.10) Asymmetric Dihydroxylation

Reagent-controlled asymmetric dihydroxylation (AD) of prochiral alkenes is feasible using chiral auxiliaries.
Sharpless and coworkers showed that treatment of prochiral alkenes with catalytic amounts of the solid, nonvolatile
dipotassium osmate dehydrate (K2[OsVIO2(OH)4]), potassium ferricyanide (K3Fe(CN)6, a stoichiometric oxidant, and a
chiral ligand results in enantioselective syn-dihydroxylation.
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The required enantiomerically pure ligands are readily available from the cinchona alkaloids dihydroquinine (DHQ) and
dehydroquinidine (DHQD).
Since use of the phthalazine spacer (PHAL) outperformed the monomeric alkaloid ligands, the (DHQ)2PHAL and
(DHQD)2PHAL analogs have become the first-choice ligands for most AD reactions.
Mechanistic studies of the origin of enantioselectivity for the cinchona alkaloidcatalyzed AD of alkenes have been
reported.

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1.11) Prevost's conditions

The formation of 1,2-diol products from alkenes can be achieved using Prevost’s reagent a solution of iodine in carbon
tetrachloride together with an equivalent of silver(I) acetate or silver(I) benzoate.
Under anhydrous conditions, this oxidant yields directly the diacyl derivative of the anti-diol (Prevost conditions),
Mechanism :

1.10) Woodward conditions:

In the presence of water the monoester of the syn-diol is obtained (Woodward conditions).
Thus, treatment of a cis-alkene with iodine and silver benzoate in boiling carbon tetrachloride under anhydrous
conditions gives the trans-dibenzoate.
With iodine and silver(I) acetate in moist acetic acid, however, the monoacetate of the cis-1,2-dihydroxy compound is
formed.
Mechanism :
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1.13) Amino-hydroxylation
Related to the dihydroxylation of alkenes with osmium tetroxide is the direct conversion of alkenes into 1,2-amino
alcohols.
Treatment of an alkene with osmium tetroxide in the presence of N-chloramine-T (TsNClNa) provides the 1,2-hydroxy
toluene-p-sulfonamide.

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