An Overview of the topic

There are several important name reactions in organic chemistry, called such because
they either bear the names of the persons who described them or else are called by a
specific name in texts and journals. Sometimes the name offers a clue about the
reactants and products, but not always.

1. Aldol Reaction or Aldol Addition

The aldol addition reaction is the combination of an alkene or ketone and

the carbonyl of another aldehyde or ketone to form a β-hydroxy aldehyde or ketone.
Aldol is a combination of the terms 'aldehyde' and 'alcohol.'

2. Aldol Condensation Reaction

The aldol condensation removes the hydroxyl group formed by the aldol addition
reaction in the form of water in the presence of a acid or base. The aldol condensation
forms α,β-unsaturated carbonyl compounds.

3. Baeyer-Villiger Oxidation - Named Organic Reactions

The Baeyer-Villiger oxidation reaction converts a ketone into an ester. This reaction
requires the presence of a peracid such as mCPBA or peroxyacetic acid. Hydrogen
peroxide can be used in conjunction with a Lewis base to form a lactone ester.

4. Baker-Venkataraman Rearrangement

The Baker-Venkataraman rearrangement reaction converts an ortho-acylated phenol

ester into a 1,3-diketone.

5. Beckmann Rearrangement Reaction

The Beckmann rearrangement reaction converts oximes into amides. Cyclic oximes will
produce lactam molecules.

6. Benzilic Acid Rearrangement

The benzilic acid Rearrangement reaction rearranges a 1,2-diketone into an α-

hydroxycarboxylic acid in the presence of a strong base.
Cyclic diketones will contract the ring by the benzilic acid rearrangement.
 7. Benzoin Condensation Reaction

The benzoin condensation reaction condenses a pair of aromatic aldehydes into an α-

hydroxyketone.

8. Friedel-Crafts Reaction

A Friedel-Crafts reaction involves the alkylation of benzene. When a haloalkane is

reacted with benzene using a Lewis acid (commonly an aluminum halide) as a catalyst,
it will attach the alkane to the benzene ring and produce excess hydrogen halide. It is
also called Friedel-Crafts alkylation of benzene.

Proper description of the named reactions

ALDOL CONDENSATION
An aldol condensation is a condensation reaction in organic chemistry in which
an enol or an enolate ion reacts with a carbonyl compound to form a β-
hydroxyaldehyde or β-hydroxyketone, followed by dehydration to give a
conjugated enone.

Aldol condensations are important in organic synthesis, because they provide a

good way to form carbon–carbon bonds. For example, the Robinson annulation
reaction sequence features an aldol condensation; the Wieland-Miescher ketone
product is an important starting material for many organic syntheses. Aldol
condensations are also commonly discussed in university level organic chemistry
classes as a good bond-forming reaction that demonstrates important reaction
mechanisms. In its usual form, it involves the nucleophilic addition of a ketone
enolate to an aldehyde to form a β-hydroxy ketone, or "aldol" (aldehyde +
alcohol), a structural unit found in many naturally occurring molecules and
pharmaceuticals.
The name aldol condensation is also commonly used, especially in biochemistry, to
refer to just the first (addition) stage of the process—the aldol reaction itself—as
catalyzed by aldolases. However, the aldol reaction is not formally a condensation
reaction because it does not involve the loss of a small molecule.

The reaction between an aldehyde/ketone and an aromatic carbonyl compound lacking

an alpha-hydrogen (cross aldol condensation) is called the Claisen-Schmidt
condensation. This reaction is named after two of its pioneering investigators Rainer
Ludwig Claisen and J. G. Schmidt, who independently published on this topic in 1880
and 1881. An example is the synthesis of dibenzylideneacetone. Quantitative yields in
Claisen-Schmidt reactions have been reported in the absence of solvent using sodium
hydroxide as the base and plus benzaldehydes.

Mechanism

The first part of this reaction is an aldol reaction, the second part a dehydration—an
elimination reaction (Involves removal of a water molecule or an alcohol molecule).
Dehydration may be accompanied by decarboxylation when an activated carboxyl
group is present. The aldol addition product can be dehydrated via two mechanisms; a
strong base like potassium t-butoxide, potassium hydroxide or sodium hydride in an
enolate mechanism, or in an acid-catalyzed enol mechanism. Depending on the nature
of the desired product, the aldol condensation may be carried out under two broad
types of conditions: kinetic control or thermodynamic control.
Condensation Types

It is important to distinguish the aldol condensation from other addition reactions of

carbonyl compounds.

 When the base is an amine and the active hydrogen compound is sufficiently
activated the reaction is called a Knoevenagel condensation.
 In a Perkin reaction the aldehyde is aromatic and the enolate generated from an
anhydride.
 A Claisen condensation involves two ester compounds.
 A Dieckmann condensation involves two ester groups in the same molecule and
yields a cyclic molecule
 A Henry reaction involves an aldehyde and an aliphatic nitro compound.
 A Robinson annulation involves a α,β-unsaturated ketone and a carbonyl
group, which first engage in a Michael reaction prior to the aldol condensation.
 In the Guerbet reaction, an aldehyde, formed in situ from an alcohol, self-
condenses to the dimerized alcohol.
 In the Japp–Maitland condensation water is removed not by an elimination
reaction but by a nucleophilic displacement

DIECKMANN CONDENSATION

The Dieckmann condensation is the intramolecular chemical reaction of diesters with

base to give β-ketoesters. It is named after the German chemist Walter Dieckmann
(1869–1925). The equivalent intermolecular reaction is the Claisen condensation.

Reaction Mechanism

Deprotonation of an ester at the α-position generates an enolate ion which then

undergoes a 5-exo-trig nucleophilic attack to give a cyclic enol. Protonation with a
Bronsted-Lowry acid (H3O+ for example) re-forms the β-keto ester.
Owing to the steric stability of five- and six-membered ring structures, these will
preferentially be formed. So 1,6 diesters will form five-membered cyclic β-keto esters,
while 1,7 diesters will form six-membered β-keto esters.

CLAISEN REARRANGEMENT

The Claisen rearrangement (not to be confused with the Claisen condensation) is a

powerful carbon–carbon bond-forming chemical reaction discovered by Rainer Ludwig
Claisenin 1912. The heating of an allyl vinyl ether will initiate a [3,3]-sigmatropic
rearrangement to give a γ,δ-unsaturated carbonyl.

The Claisen rearrangement is the first recorded example of a [3,3]-sigmatropic

rearrangement.

The Claisen rearrangement is an exothermic, concerted (bond cleavage and

recombination) pericyclic reaction. Woodward–Hoffmann rules show a suprafacial,
stereospecific reaction pathway. The kinetics are of the first order and the whole
transformation proceeds through a highly ordered cyclic transition state and is
intramolecular. Crossover experiments eliminate the possibility of the rearrangement
occurring via an intermolecular reaction mechanism and are consistent with an
intramolecular process.

There are substantial solvent effects observed in the Claisen rearrangement, where
polar solvents tend to accelerate the reaction to a greater extent. Hydrogen-bonding
solvents gave the highest rate constants. For example, ethanol/water solvent mixtures
give rate constants 10-fold higher than sulfolane. Trivalent organoaluminium reagents,
such as trimethylaluminium, have been shown to accelerate this reaction.

The first reported Claisen rearrangement is the [3,3]-sigmatropic rearrangement of an

allylphenyl ether to intermediate 1, which quickly tautomerizes to an ortho-substituted
phenol.

Meta-substitution affects the regioselectivity of this rearrangement. For example,

electron withdrawing groups (e.g. bromide) at the meta-position direct the
rearrangement to the ortho-position (71% ortho-product), while electron donating
groups (e.g. methoxy), direct rearrangement to the para-position (69% para-product).
Additionally, presence of ortho-substituents exclusively leads to para-substituted
rearrangement products (tandem Claisen and Cope rearrangement).

If an aldehyde or carboxylic acid occupies the ortho or para positions, the allyl side-
chain displaces the group, releasing it as carbon monoxide or carbon dioxide,
respectively.

Bellus–Claisen rearrangement

The Bellus–Claisen rearrangement is the reaction of allylic ethers, amines, and

thioethers with ketenes to give γ,δ-unsaturated esters, amides, and thioesters. This
transformation was serendipitously observed by Bellus in 1979 through their synthesis
of a key intermediate of an insecticide, pyrethroid. Halogen substituted ketenes (R1, R2)
are often used in this reaction for their high electrophilicity. Numerous reductive
methods for the removal of the resulting α-haloesters, amides and thioesters have been
developed. The Bellus-Claisen offers synthetic chemists a unique opportunity for ring
expansion strategies.

Eschenmoser–Claisen rearrangement

The Eschenmoser–Claisen rearrangement proceeds by heating allylic alcohols in the

presence of N,N-dimethylacetamide dimethyl acetal to form γ,δ-unsaturated amide.
This was developed by Albert Eschenmoser in 1964. Eschenmoser-Claisen
rearrangement was used as a key step in the total synthesis of morphine.

Ireland–Claisen rearrangement

The Ireland–Claisen rearrangement is the reaction of an allylic carboxylate with a strong

base (such as lithium diisopropylamide) to give a γ,δ-unsaturated carboxylic acid. The
rearrangement proceeds via silylketene acetal, which is formed by trapping the lithium
enolate with chlorotrimethylsilane. Like the Bellus-Claisen (above), Ireland-Claisen
rearrangement can take place at room temperature and above. The E- and Z-configured
silylketene acetals lead to anti and syn rearranged products, respectively. There are
numerous examples of enantioselective Ireland-Claisen rearrangements found in
literature to include chiral boron reagents and the use of chiral auxiliaries.
Johnson–Claisen rearrangement

The Johnson–Claisen rearrangement is the reaction of an allylic alcohol with an

orthoester to yield a γ,δ-unsaturated ester. Weak acids, such as propionic acid, have
been used to catalyze this reaction. This rearrangement often requires high
temperatures (100 to 200 °C) and can take anywhere from 10 to 120 hours to complete.
However, microwave assisted heating in the presence of KSF-clay or propionic acid
have demonstrated dramatic increases in reaction rate and yields.

Mechanism:
Photo-Claisen rearrangement

The photo-Claisen rearrangement is closely related to the photo-Fries rearrangement,

that proceeds through a similar radical mechanism. Aryl ethers undergo the photo-
Claisen rearrangement, while the photo-Fries rearrangement utilizes aryl esters.

Hetero-Claisens

Aza–Claisen

An iminium can serve as one of the pi-bonded moieties in the rearrangement.

Chromium oxidation

Chromium can oxidize allylic alcohols to alpha-beta unsaturated ketones on the

opposite side of the unsaturated bond from the alcohol. This is via a concerted hetero-
Claisen reaction, although there are mechanistic differences since the chromium atom
has access to d- shell orbitals which allow the reaction under a less constrained set of
geometries.
Chen–Mapp reaction

The Chen–Mapp reaction also known as the [3,3]-Phosphorimidate Rearrangement or

Staudinger–Claisen Reaction installs a phosphite in the place of an alcohol and takes
advantage of the Staudinger reduction to convert this to an imine. The subsequent
Claisen is driven by the fact that a P=O double bond is more energetically favorable
than a P=N double bond.

Overman rearrangement

The Overman rearrangement (named after Larry Overman) is a Claisen rearrangement

of allylic trichloroacetimidates to allylic trichloroacetamides.

Overman rearrangement is applicable to synthesis of vicinol diamino comp from 1,2

vicinal allylic diol.

Zwitterionic Claisen rearrangement

Unlike typical Claisen rearrangements which require heating, zwitterionic Claisen

rearrangements take place at or below room temperature. The acyl ammonium ions are
highly selective for Z-enolates under mild conditions
Claisen rearrangement in nature

The enzyme Chorismate mutase (EC 5.4.99.5) catalyzes the Claisen rearrangement of
chorismate ion to prephenate ion, a key intermediate in the shikimic acid pathway (the
biosynthetic pathway towards the synthesis of phenylalanine and tyrosine).

The Claisen condensation is a carbon–carbon bond forming reaction that occurs

between two esters or one ester and another carbonyl compound in the presence of a
strong base, resulting in a β-keto ester or a β-diketone. It is named after Rainer Ludwig
Claisen, who first published his work on the reaction in 1887.

Requirements

At least one of the reagents must be enolizable (have an α-proton and be able to
undergo deprotonation to form the enolate anion). There are a number of different
combinations of enolizable and nonenolizable carbonyl compounds that form a few
different types of Claisen condensations.

The base used must not interfere with the reaction by undergoing nucleophilic
substitution or addition with a carbonyl carbon. For this reason, the conjugate sodium
alkoxide base of the alcohol formed (e.g. sodium ethoxide if ethanol is formed) is often
used, since the alkoxide is regenerated. In mixed Claisen condensations, a non-
nucleophilic base such as lithium diisopropylamide, or LDA, may be used, since only
one compound is enolizable. LDA is not commonly used in the classic Claisen or
Dieckmann condensations due to enolization of the electrophilic ester.

The alkoxy portion of the ester must be a relatively good leaving group. Methyl and
ethyl esters, which yields methoxide and ethoxide, respectively, are commonly used.

Types

 The classic Claisen condensation, a self-condensation between two molecules of a

compound containing an enolizable ester.

 The mixed (or "crossed") Claisen condensation, where one enolizable ester or
ketone and one nonenolizable ester are used.

 The Dieckmann condensation, where a molecule with two ester groups reacts
intramolecularly, forming a cyclic β-keto ester. In this case, the ring formed must
not be strained, usually a 5- or 6-membered chain or ring.

Mechanism
In the first step of the mechanism, an α-proton is removed by a strong base, resulting in
the formation of an enolate anion, which is made relatively stable by the delocalization
of electrons. Next, the carbonyl carbon of the (other) ester is nucleophilically attacked
by the enolate anion. The alkoxy group is then eliminated (resulting in (re)generation of
the alkoxide), and the alkoxide removes the newly formed doubly α-proton to form a
new, highly resonance-stabilized enolate anion. Aqueous acid (e.g. sulfuric acid or
phosphoric acid) is added in the final step to neutralize the enolate and any base still
present. The newly formed β-keto ester or β-diketone is then isolated. Note that the
reaction requires a stoichiometric amount of base as the removal of the doubly α-proton
thermodynamically drives the otherwise endergonic reaction. That is, Claisen
condensation does not work with substrates having only one α-hydrogen because of the
driving force effect of deprotonation of the β-keto ester in the last step.

Stobbe condensation

The Stobbe condensation is a modification specific for the diethyl ester of succinic acid
requiring less strong bases. An example is its reaction with benzophenone:

A reaction mechanism that explains the formation of both an ester group and a
carboxylic acid group is centered on a lactone intermediate (5):
The Wittig reaction or Wittig olefination is a chemical reaction of an aldehyde or ketone
with a triphenyl phosphonium ylide (often called a Wittig reagent) to give an alkene
and triphenylphosphine oxide.

The Wittig reaction was discovered in 1954 by Georg Wittig, for which he was awarded
the Nobel Prize in Chemistry in 1979. It is widely used in organic synthesis for the
preparation of alkenes. It should not be confused with the Wittig rearrangement.

Wittig reactions are most commonly used to couple aldehydes and ketones to singly
substituted phosphine ylides. With unstabilised ylides this results in almost exclusively
the Z-alkene product. In order to obtain the E-alkene, stabilised ylides are used or
unstabilised ylides using the Schlosser modification of the Wittig reaction can be
performed.

Reaction mechanism

Classical mechanism

The steric bulk of the ylide 1 influences the stereochemical outcome of nucleophilic
addition to give a predominance of the betaine 3 (cf. Bürgi–Dunitz angle). Note that for
betaine 3 both R1 and R2 as well as PPh3+ and O− are positioned anti to one another.
Carbon-carbon bond rotation gives the betaine 4, which then forms the
oxaphosphetane 5. Elimination gives the desired Z-alkene 7 and
triphenylphosphine oxide 6. With simple Wittig reagents, the first step occurs easily
with both aldehydes and ketones, and the decomposition of the betaine (to form 5) is
the rate-determining step. However, with stabilised ylides (where R1 stabilises the
negative charge) the first step is the slowest step, so the overall rate of alkene formation
decreases and a bigger proportion of the alkene product is the E-isomer. This also
explains why stabilised reagents fail to react well with sterically hindered ketones.

Mechanism

Mechanistic studies have focused on unstabilized ylides, because the intermediates can
be followed by NMR spectroscopy. The existence and interconversion of the betaine
(3a and 3b) is subject of ongoing research. Phosphonium ylides 1 react with carbonyl
compounds 2 via a π²s/π²a [2+2] cycloaddition to directly form the
oxaphosphetanes 4a and 4b. The stereochemistry of the product 5 is due to the addition
of the ylide 1 to the carbonyl 2 and to the equilibration of the intermediates. Maryanoff
and Reitz identified the issue about equilibration of Wittig intermediates and termed
the process "stereochemical drift". For many years, the stereochemistry of the Wittig
reaction, in terms of carbon-carbon bond formation, had been assumed to correspond
directly with the Z/E stereochemistry of the alkene products. However, certain
reactants do not follow this simple pattern. Lithium salts can also exert a profound
effect on the stereochemical outcome.
Mechanisms differ for aliphatic and aromatic aldehydes and for aromatic and aliphatic
phosphonium ylides. Evidence suggests that the Wittig reaction of unbranched
aldehydes under lithium-salt-free conditions do not equilibrate and are therefore under
kinetic reaction control. Vedejs has put forth a theory to explain the stereoselectivity of
stabilized and unstabilized Wittig reactions.

Wittig reagents

Preparation of phosphorus ylides

Wittig reagents are usually prepared from a phosphonium salt, which is in turn
prepared by the quaternization of triphenylphosphine with an alkyl halide. The
alkylphosphonium salt is deprotonated with a strong base such as n-butyllithium:

One of the simplest ylides is methylenetriphenylphosphorane (Ph3P=CH2). It is also a

precursor to more elaborate Wittig reagents. Alkylation of Ph3P=CH2 with a primary
alkyl halide R−CH2−X, produces substituted phosphonium salts:

These salts can be deprotonated in the usual way to give Ph3P=CH−CH2R.

Structure of the ylide

 Ball-and-stick model of Ph3P=CH2, as found in the
crystal structure

The Wittig reagent may be described in the phosphorane form (the more familiar
representation) or the ylide form:

The ylide form is a significant contributor, and the carbon is nucleophilic.

Reactivity

Simple phosphoranes are reactive. Most hydrolyze and oxidize readily. They are
therefore prepared using air-free techniques. Phosphoranes are more air-stable when
they contain an electron withdrawing group. Some examples are Ph3P=CHCO2R and
Ph3P=CHPh. These ylides are sufficiently stable to be sold

commercially

From the phosphonium salts, these reagent are formed more readily, requiring only
NaOH, and they are usually more air-stable. These are less reactive than simple ylides,
and so they usually fail to react with ketones, necessitating the use of the Horner–
Wadsworth–Emmons reaction as an alternative. They usually give rise to an E-alkene
product when they react, rather than the more usual Z-alkene.

Scope and limitations

The Wittig reaction is a popular method for the synthesis of alkene from ketones and
aldehydes. The Wittig reagent can generally tolerate carbonyl compounds containing
several kinds of functional groups such as OH, OR, aromatic nitro and even ester
groups. There can be a problem with sterically hindered ketones, where the reaction
may be slow and give poor yields, particularly with stabilized ylides, and in such cases
the Horner–Wadsworth–Emmons (HWE) reaction (using phosphonate esters) is
preferred. Another reported limitation is the often labile nature of aldehydes which can
oxidize, polymerize or decompose. In a so-called Tandem Oxidation-Wittig Process the
aldehyde is formed in situ by oxidation of the corresponding alcohol.

As mentioned above, the Wittig reagent itself is usually derived from a primary alkyl
halide. Quaternization of triphenylphosphine with most secondary halides is inefficient.
For this reason, Wittig reagents are rarely used to prepare tetrasubstituted alkenes.
However the Wittig reagent can tolerate many other variants. It may contain alkenes
and aromatic rings, and it is compatible with ethers and even ester groups. Even C=O
and nitrile groups can be present if conjugated with the ylide- these are the stabilised
ylides mentioned above. Bis-ylides (containing two P=C bonds) have also been made
and used successfully.

One limitation relates to the stereochemistry of the product. With simple ylides, the
product is usually mainly the Z-isomer, although a lesser amount of the E-isomer is
often formed also – this is particularly true when ketones are used. If the reaction is
performed in DMF in the presence of LiI or NaI, the product is almost exclusively the Z-
isomer. If the E-isomer is the desired product, the Schlosser modification may be used.
With stabilised ylides the product is mainly the E-isomer, and this same isomer is also
usual with the HWE reaction.

Schlosser modification
The major limitation of the traditional Wittig reaction is that the reaction proceeds
mainly via the erythro betaine intermediate, which leads to the Z-alkene. The erythro
betaine can be converted to the threo betaine using phenyllithium at low temperature.
This modification affords the E-alkene.

Allylic alcohols can be prepared by reaction of the betaine ylid with a second
aldehyde. For example:
Examples

Because of its reliability and wide applicability, the Wittig reaction has become a
standard tool for synthetic organic chemists.

The most popular use of the Wittig reaction is for the introduction of a methylene group
using methylenetriphenylphosphorane (Ph3P=CH2). Using this reagent even a sterically
hindered ketone such as camphor can be converted to its methylene derivative. In this
case, the Wittig reagent is prepared in situ by deprotonation of
methyltriphenylphosphonium bromide with potassium tert-butoxide. In another
example, the phosphorane is produced using sodium amide as a base, and this reagent
converts the aldehyde shown into alkene I in 62% yield. The reaction is performed in
cold THF, and the sensitive nitro, azo and phenoxide groups are tolerated. The product
can be used to incorporate a photostabiliser into a polymer, to protect the polymer from
damage by UV radiation.
Another example of its use is in the synthesis of leukotriene A methyl ester. The first
step uses a stabilised ylide, where the carbonyl group is conjugated with the ylide
preventing self condensation, although unexpectedly this gives mainly the cis product.
The second Wittig reaction uses a non-stabilised Wittig reagent, and as expected this
gives mainly the cis product. Note that the epoxide and ester functional groups survive
intact.

Methoxymethylenetriphenylphosphine is a Wittig reagent for the homologation of

aldehydes.

References

1. Schaefer, J. P.; Bloomfield, J. J. (1967). "The Dieckmann Condensation (Including the

Thorpe-Ziegler Condensation)". Organic Reactions. 15: 1–
203. doi:10.1002/0471264180.or015.01.
2. Davis, B. R.; Garrett, P. J. Comp. Org. Syn. 1991, 2, 806-829. (Review)
3. Janice Gorzynski Smith (2007). Organic Chemistry (2nd ed.). pp. 932–933. ISBN 978-
0073327495.
4. "Dieckmann Condensation". Organic Chemistry Portal.
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