Presented by Dhanashree Kavhale. M. Pharm.(Pharmaceutical Chemistry) 1st year. Various organic named reactions are there in Advanced Organic Chemistry I, as some of them are explained along with their mechanism.

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…