1. Named Reactions

2. Index
1. Ugi Reaction
2. Brook Rearrangement
3. Ullman Coupling Reactions
4. Dieckmann Reaction
5. Doebner-Miller Reaction
6. Sandmeyer Reaction
7. Michael Addition Reaction

3. Ugi Reaction
 The Ugi reaction was first reported by I. Ugi in 1959.
 it is classified as an isocyanide-based multicomponent
reaction.
 The reaction is usually conducted in a polar protic solvent
such as methanol, and some success in water has been
shown.
 non-polar halogenated solvents prove detrimental, as
most amines are insoluble, favoring the occurrence of the
Passerini reaction.
 Ugi reaction is a multi-component reaction in organic
chemistry involving a ketone or aldehyde, an amine, an
isocyanide and a carboxylic acid to form a bis-amide.

4.  A multicomponent reaction (MCR) is generally defined as any process
in which three or more reactants combine in one pot to form a
product that incorporates structural features of each reagent.
 Mechanism of Ugi reaction :
1. Imine formation with amine v/s ketone.
2. Proton exchange ( forming iminium ion)
3. Nucleophilic addition of isocyanide.
4. Nucleophilic addition of carboxylic acid anion.
5. Numm’s Rearrangement.

5. Applications :
1. The Ugi reaction is one of the first reactions to be exploited explicitly
to develop chemical libraries. Eg: Isoquinolines from Ugi.
2. Additionally, many of the caine-type anesthetics are synthesized using
this reaction.

6. Sandmeyer Reaction
 synthesis aryl halides from aryl diazonium salts using copper salts as
reagents or catalysts.
 The Sandmeyer reaction is an example of a radical-nucleophilic
aromatic substitution (SRNAr).
 Sandmeyer reaction is unique one as we can do transformation of
benzene such as halogenation, trifluoromethylation, hydroxylation
etc.

7. Mechanism of Sandmeyer's reaction :
1.Formation of nitrosonium ion:
2. Formation of benzodiazonium ion:
3. Single electron transfer and formation of aryl halide :

8. Application of Sandmeyer's Reaction:
1. Used for synthesis of aryl halides.
2. For Cynation eg: synthesis of fluanxol and Neoamphimedine.
3. Trifluoromethylation : Sandmeyer-type reactions can be used to
generate aryl compounds functionalized by trifluoromethyl
substituent groups.
4. For hydroxylation process.

9. Brook Rearrangement
 The rearrangement was first observed in the late 1950s by Canadian
chemist Adrian Gibbs Brook.
 In organic chemistry the Brook rearrangement refers to any [1,n]
carbon to oxygen silyl migration.
 It this reaction an organosilyl group switches position with the
hydrogen proton over a carbon to oxygen covalent bond under the
influence of base.

10. Mechanism of Brooks rearrangement:
Applications of Brook Rearrangement:
1. K.takede and co-workers synthesized the tricyclic core of cyanthins.
2. Developed an new synthetic strategy for the stereoselective
construction of 8 membered carbocyclic compound.

11. Ullman Coupling Reaction
 The Ullmann reaction is an organic named reaction that involves the
coupling of two aryl halides in the presence of copper to yield a biaryl
as the product.
 Traditionally this reaction is affected by copper, but palladium and
nickel are also effective catalysts.
 General reaction is illustrated below:

12. mechanism of the Ullmann reaction:
 formation of an active copper(I) species upon the introduction of the
aryl halide to an excess of metallic copper under relatively high
temperatures.
 This copper(I) species undergoes further oxidative addition with
another haloarene molecule, linking the two molecules.

13.  the copper compound formed by the two aryl halide molecules
undergoes reductive elimination, resulting in the formation of a new
carbon-carbon bond between the two aryl compounds.
 Applications:
1. Biphenylenes can be obtained from 2,2-diiodobiphenyl.
2. employed for the closure of five-membered rings.
3. Chiral reactants can be coupled into a chiral product via this reaction.

14. Doebner-Miller Reaction
 This reaction is generally used for the synthesis of Quinolines with
substituents on the pyridinoid ring.
 The Doebner–Miller reaction is the organic reaction of an aniline with
α,β-unsaturated carbonyl compounds to form quinolines.
 his reaction is also known as the Skraup-Doebner-Von Miller quinoline
synthesis.

15. Mechanism of Doebner-Miller Reaction :
Applications:
1. synthesis of quinolines with substituents on the pyridinoid ring.

16. Dieckman Reaction
 The Dieckman condensation is the intramolecular chemical reaction of
diesters with base to give β-keto esters.
 named after the German chemist Walter Dieckman. The equivalent
intermolecular reaction is the Claisen condensation.

17. Mechanism of Dieckman reaction:

18.  Applications of Dieckman reaction:
1. Dieckman condensation has been used to form five and six-membered
rings in a number of synthesis of natural products.
such as α-pinene, oestrone, cyclic indole, and so on.

19. Michael Addition Reaction
 The Michael reaction is a nucleophilic addition reaction involving the
addition of a carbanion (or any other suitable nucleophile) to an 𝛼,𝛽-
unsaturated carbonyl compound that contains a functional group
which is electron-withdrawing in nature.
 It belongs to the larger class of conjugate additions and is widely used
for the mild formation of carbon-carbon bonds.
Michael donor Michael acceptor

20.  Mechanism:
1. formation of nucleophile.
2. Conjugate addition of nu- to α- β unsaturated carbonyl compound.
3. Protonation.

21.  Applications:
1. Michael addition to form a seven-membered oxazepane ring.
2. Used in preparation of di,tri, carboxylic acids.
3. Preparation of ketones and diketones.
4. Preparation of cyclopropane derivatives.

22. References
 Nelson, T. D.; Crouch, R. D. (2004). "Cu, Ni, and Pd Mediated
Homocoupling Reactions in Biaryl Syntheses: The Ullmann Reaction".
Org. React. 63: 265. doi:10.1002/0471264180.or063.03. ISBN
0471264180.
 Areces P, Gil MV, Higes FJ, Román E, Serrano JA. Stereoselective
Michael addition reactions of 5-glyco-4-nitrocyclohex-1-enes.
Tetrahedron letters. 1998 Nov 12;39(46):8557-60.
 Ugi I, Lohberger S, Karl R. The Passerini and Ugi Reactions.
 Oprea TI, Gottfries J, Sherbukhin V, Svensson P, Kühler TC. Chemical
information management in drug discovery: optimizing the
computational and combinatorial chemistry interfaces. Journal of
Molecular Graphics and Modelling. 2000 Jan 1;18(4-5):512-24.
 Naganuma K, Kawashima T, Okazaki R. Control Factors of Two
Reaction Modes of Pentacoordinate 1, 2-Oxasiletanides, the Peterson
Reaction and Homo-Brook Rearrangement. Chemistry Letters. 1999
Nov;28(11):1139-40.

23. Thank you…