ORGANIC

CHEMISTR
Y

ORGANIC
CHEMISTRY
Named Organic
Lecture
Reactions : : 18
 WITTIG REACTION
Aldehydes and ketones react with phosphorus ylides to yield alkenes
and triphenylphosphine oxide (a by-product). This reaction is known
as the Wittig reaction.
• Georg Wittig discovered Wittig reaction and his reaction proved so
useful that Wittig received the Nobel Prize in chemistry in 1979 for
this discovery .
• the Wittig reaction converts the carbonyl group of a ketone or an
aldehyde into a new C=C double bond where no bond existed
before.
 WITTIG REACTION
• Wittig reactions may be carried out in a number of different
solvents; normally tetrahydrofuran (THF) or dimethyl sulfoxide
(DMSO) is used

PHOSPHORUS YLIDES :
• A molecule that bears no overall charge but has a negatively charged
carbon atom bonded to a positively charged heteroatom .
• In an ylide such as , phosphorus has eight electrons and
is positively charged; its attached carbon has eight electrons and is
negatively charged.
• so we can say that ylide is a phosphorus-stabilized carbanion.
 WITTIG REACTION
FORMATION OF YLIDE :
• The phosphonium ylide needed for a particular synthesis is obtained
by an reaction between triphenylphosphine and an alkyl halide with
the appropriate number of carbon atoms.
• phosphorus ylides are prepared from triphenylphosphine and alkyl
halides in a two-step process.
i. The first reaction is a nucleophilic substitution reaction.
• Triphenylphosphine is an excellent nucleophile and a weak base. It
reacts readily with 1° and 2° (unhindered) alkyl halides by an SN2
mechanism to displace a halide ion from the alkyl halide to give an
alkyltriphenylphosphonium salt.
 WITTIG REACTION
ii. The second reaction is an acid–base reaction.
• A strong base (usually an alkyllithium or phenyllithium) removes a
proton from the carbon that is attached to phosphorus to give the
ylide.
• Suitable strong bases include the sodium salt of dimethyl sulfoxide
(in dimethyl sulfoxide as the solvent) and organolithium reagents (in
diethyl ether or tetrahydrofuran).
• Phosphorus atoms, especially those that are positively charged or
that carry electronegative substituents, can increase the acidity of
protons adjacent to them on the carbon skeleton.
• Phosphonium salts can therefore be deprotonated by a moderately
strong base to give a species known as an ylide, carrying (formally) a
positive and a negative charge on adjacent atoms.
 WITTIG REACTION
A specific example is given as

Resonance in YLIDE:
• The phosphorus ylide has two resonance forms:
• one with a double bond between carbon and phosphorus, and
another with charges on carbon and phosphorus.
 WITTIG REACTION
• The double-bonded resonance form requires ten electrons in the valence
shell of phosphorus, using a d orbital.
• The pi bond between carbon and phosphorus is weak, and the charged
structure is the major contributor.
• The carbon atom actually bears a partial negative charge, balanced by a
corresponding positive charge on phosphorus.
MECHANISM OF WITTIG REACTION :
The mechanism consists of following steps.
• Because of its carbanion character, the ylide carbon atom is strongly
nucleophilic. It attacks a carbonyl group to give a charge-separated
intermediate called a betaine
• A betaine is an unusual compound because it contains a negatively
charged oxygen and a positively charged phosphorus on adjacent
carbon atoms.
• Phosphorus and oxygen form strong bonds, and the attraction of
opposite charges promotes the fast formation of a four-membered
oxaphosphetane ring.
 WITTIG REACTION
• Mostly the oxaphosphetane may be formed directly by a
cycloaddition, rather than via a betaine.
• The four-membered ring quickly collapses to give the alkene and
triphenylphosphine oxide.
• Triphenylphosphine oxide is exceptionally stable, and the conversion
of triphenylphosphine to triphenylphosphine oxide provides the
driving force for the Wittig reaction.
• Mixtures of cis and trans isomers often result when geometric
isomerism is possible
WITTIG REACTION
 WITTIG REACTION
• Alternative mechanism not involving betaine is also widely accepted
.
 WITTIG REACTION
Regioselctivity : Position of double bond.
• The Wittig reaction is a very powerful way to make an alkene
because the reaction is completely regioselective—the double bond
will be in only one place.

Stereo selectivity:
• The stereoselectivity of the Wittig reaction depends on the structure
of the ylide
• Ylides can be divided into two types:
a. Stabilized ylides have a group, such as a carbonyl group, that can
share the carbanion’s negative charge
b. unstabilized ylides do not have such a group.
 WITTIG REACTION
• Stabilized ylides form primarily E isomers
• unstabilized ylides form primarily Z isomers
 WITTIG REACTION
How to Plan a Wittig Synthesis :
• Planning a Wittig synthesis begins with recognizing in the desired
alkene
• what can be the aldehyde or ketone component ?
• what can be the halide component ?
• In general, the ylide should come from an unhindered alkyl halide.
• Triphenylphosphine is a bulky reagent, reacting best with
unhindered primary and methyl halides. It occasionally reacts with
unhindered secondary halides, but these reactions are sluggish and
often give poor yields .
• (Recall that the more sterically hindered the alkyl halide, the less
reactive it is in an SN1 reaction )
 WITTIG REACTION
• Examples:
 WITTIG REACTION
Advantages and Applications :
• The Wittig reaction also is the best way to make a terminal alkene
such as methylenecyclohexane because other methods would form
a terminal alkene only as a minor product if at all.
 WITTIG REACTION
• The most attractive feature of the Wittig reaction is its
regiospecificity. The location of the double bond is never in doubt.
• This is in contrast to E1 eliminations, which may yield multiple
alkene products by rearrangement to more stable carbocation
intermediates, and both E1 and E2 elimination reactions, which may
produce multiple products when different b hydrogens are
available for removal.
WITTIG REACTION
 WITTIG REACTION
• How would you synthesize these?
 WITTIG REACTION
How to plan synthesis of 3- i. Now , attach carbonyl group
methyl-2-pentene via Wittig and triphenylphosphine
Reaction? with each part ,
i. Step one : split the molecule alternatively.
into two halves , by to form aldehyde/ketone
splitting the double bond. and
You will get and ylide , respectively
 WITTIG REACTION
iii. Now give reactants for the formation of above mentioned
ylides:

iv. The preferred method will be one , involving less hindered alkyl
halide for the formation of ylide.
• Method involving n-propylbromide will be preferred.
 d
Preferred Metho