Iodine–Silver Benzoate — the Prévost Reaction

In the Prévost reaction, an alkene is treated with 1 mol equiv. of iodine and 2 mol equiv. of
silver carboxylate (most often silver benzoate) in an inert solvent (for example, benzene),
leading to formation of a racemic mixture of 1,2-diesters 

The reaction proceeds through initial formation of a complex (the Simonini complex),
which can itself be prepared and isolated separately, prior to use in such a
reaction. Anti addition of the ArCOO- to the alkene through a cyclic iodonium ion gives the
1-acyloxy-2-iodo compound, and displacement of iodide ion with anchimeric assistance by
the neighboring acyloxy group affords the 1,3-dioxolan-2-ylium ion . Nucleophilic attack by
carboxylate anion on then leads to diesters. Hydrolysis of the latter yields a mixture of the
corresponding 1,2-diols with stereochemistry corresponding to anti hydroxylation of the
alkene
Woodward Hydroxylation is the synthesis of syn-diols or cis-diols from
alkenes. This reaction is named after an American organic chemist, Robert Burns
Woodward. When alkene is treated with iodine and silver acetate, it will undergo
nucleophilic displacement with acetate in the presence of water. The intermediate product
gives the desired diols on hydrolysis.
Woodward reaction of an anion with a double bond may be regarded as close to an SN2
displacement – one of the two bonds of that double bond being displaced, by backside
attack with the stereochemistry that is hard in
Woodward Reaction Mechanism
The woodward reaction allows the synthesis of
syn-diols from alkenes by the addition of iodine
followed by nucleophilic displacement with
acetate in the presence of water. Hydrolysis of
the intermediate ester gives the desired diol.
The steps involved in the mechanism of
woodward reaction are listed below.
1.Iodine reacts with alkene forming a cyclic
iodonium intermediate.
2.Further, the cyclic intermediate reacts with
acetate ion in SN2 fashion to form a five-
membered ring compound.
3.The five-membered rings are opened by 
Hydrolysis reaction.
4.Further protonation followed by hydrolysis
gives the corresponding diols.
 What is Oppenauer Oxidation
Oppenauer Oxidation is the process of conversion of secondary alcohols to ketones by
selective oxidation. This reaction is named after Rupert Viktor Oppenauer. Oxidation
reaction takes place in the presence of [Al(i-Pro)3] in excess of acetone.
It is an aluminium alkoxide catalyzed the oxidation of a secondary alcohol to the
corresponding ketone. This is reverse of the Meerwein Ponndorf Verley reduction. It is a very
good method to oxidise allylic alcohols to α, β- unsaturated ketones.
 Riley reaction:
The Riley oxidation is a selenium dioxide-mediated oxidation of methylene groups
adjacent to carbonyls. It was first reported by Riley 
Selenium dioxide can perform several common types of oxidations, such
as alcohols to ketones and aldehydes, as well as dehydrogenation of
ketones to enones. Because of its toxicity, and the sometimes
malodorous selenium-containing byproducts formed, SeO2 is used only
where it competes well with other methods, or provides unique
reactivity. One of these is the allylic oxidation of alkenes to allylic
alcohols with regiocontrol (without migration of the double bond), and a
second is the α-oxidation of ketones to α-diketones (only effective if
there are no β-hydrogens).
Mechanism:
Assignment: (10)
Q.No.1: Write a short note on following
oxidizing agent:
(I) PCC (II)Tollen’s reagent (III) Benedict
reagent
(IV) haloform (V) HNO3 (VI) Jone’s reagent