InCl3 CATALYZED ONE-POT

ORGANIC SYNTHESIS

Presented by:-

ABDUL MOTALEB

AMU,ALIGARH

EN No: GD4872

CONTENTS

INTRODUCTION

PREPARATION AND PROPERTIES OF InCl3

ADVANTAGES OF InCl3

MULTICOMPONENT REACTIONS

InCl3 PROMOTED ORGANIC SYENTHESIS

APPLICATIONS

CONCLUSION

REFERENCES

INTRODUCTION

Presentation aims to illustrate the progress in a large variety of InCl3 catalyzed reactions performed in solvent and solvent free conditions.

Synthetic potential of InCl3 mediated reactions, which have recently emerged as useful strategy in organic synthesis.

A variety of two component and multicomponent reactions catalyzed by InCl3 that led to the production of structurally diverse compounds under mild reaction conditions.

CONT…

Study of the InCl3 catalyzed chemistry have been

the object of an interest which include the

development of new synthetic strategies, the

optimization of reaction conditions and the

application to the synthesis of bioactive

derivatives.

Ref: Yadav, J. S.; Aneesh, A.; Jimil, G.; Reddy, B. V. S. Eur. J. Org. Chem. 2010, 591.

PREPARATION AND PROPERTIES OF

InCl3

InCl3 is prepared by the reaction of indium with

chlorine by gentle warming.

2In +3Cl2 2InCl3

InCl3 is a white, odorless, and highly deliquescent

powder.

Its particles are flake or plate-shaped and highly

soluble in water and mineral acids.

ADVANTAGES OF InCl3

Development of practical catalysts for efficient synthesisis of key importance to both academia and the chemicalindustry.

Lewis acid catalysis has attracted much attention inorganic synthesis. These Lewis acids generally must beused under strictly anhydrous conditions. The mostactive Lewis acids such as BF3, TiCl4 and AlCl3 reactviolently with water and can not be used under aqueousconditions.

In addition, recovery and reuse of the conventionalLewis acids are also formidable tasks. Thesedisadvantages have restricted the use of Lewis acids inorganic synthesis under aqueous media.

CONT…Some advantages are as follows

Compatibility both to aqueous and organic solvent

Water stability And Recyclability

Highly chemo, regio and stereoselective.

Operational simplicity

A strong tolerance to oxygen and nitrogen containingsubstrates and functional groups.

Its lower heterophilicity makes it an ideal catalyst forthe C-C bond formation reactions.

Harmless and environment friendly.

InCl3 is not only compatible with water but alsocheaper than other indium salts.

Ref: Braga, A. L.; Schneider, P. H.;Paixao, M. W.; Deobald, A. M. Tetrahedron Lett. 2006, 47, 7195;

MULTICOMPONENT REACTIONS

Multicomponent reactions (MCRs) has emerged as apowerful tool in synthetic chemistry for the rapidgeneration of molecular complexity and diversity.

Among the various methods of bond formation andbond cleavages, multicomponent reactionsundoubtedly occupy a prime position in organicsynthesis -

Primarily due to their convergent nature.

Superior atom-economy.

Straightforward experimental procedure.

Ref: Adib, M.; Sheikhi, E.; Kavoosi, A.; Bijanzadeh, H. R. Tetrahedron 2010, 66, 9263.

InCl3 PROMOTED ORGANIC

SYENTHESIS Coupling of Aldehydes, Alkynes and Amines

Synthesis of 1,3,5-tri-substituted benzenes

Synthesis of 1,8-naphthyridines

Synthesis of carbonyl compounds

Synthesis of dihydropyranochromenediones

Synthesis of coumarin derivatives

InCl3-catalyzed Diels-Alder reaction, Friedel-crafts reaction, Mannich reaction

One-pot synthesis of quinolines

Michael addition reaction

Synthesis of functionalized benzof chromenes

COUPLING OF ALDEHYDES,

ALKYNES AND AMINES

Ref: Zhang, Y.; Li, P.; Wang, M.; Wang, L. J. Org. Chem. 2009, 74, 4364.

SYNTHESIS OF 1,3,5-TRI-

SUBSTITUTED BENZENES

Ref: Xu, Y.-L.; Pan, Y.-M.; Wu, Q.; Wang, H.-S.; Liu, P.-Z. J. Org. Chem. 2011, 76, 8472.

InCl3

InCl3-CATALYZED FRIEDEL-

CRAFTS REACTION

Ref: Miyai, T.; Onishi, Y.; Baba, A. Tetrahedron Lett. 1998, 39, 6291;

+

SYNTHESIS OF

DIHYDROPYRANOCHROMENEDIONES

Ref: Reddy, B. V. S.; Reddy, M. R.; Narasimhulu, G.; Yadav, J. S. Tetrahedron Lett. 2010, 51, 5677.

+

ONE-POT SYNTHESIS OF

QUINOLINES

Ref: Ranu, B. C.; Hajra, A.; Dey, S. S.; Jana, U. Tetrahedron 2003, 59, 813;

AROMATIZATION

MUKAIYAMA-MICHEAL TYPE

REACTION

Ref: Chua, S.-S.; Alni, A.; Chan, L.-T. J.; Yamane, M.; Loh, T.-P. Tetrahedron 2011, 67,

5079.

SYNTHESIS OF COUMARINS

DERIVATIVES

Ref: Verma, R. K.; Verma, G. K.; Shukla, G.; Singh, M. S. RSC Adv. 2012, 2, 2413.

CONCLUSIONS

The result summarized in this presentation clearly indicatethat there has been continues to be substantial interest in theorganic transformation promoted by indium chloride.

InCl3 is being routinely used todays preparation in simple tocomplex molecules and we described the importance ofindium chloride in the construction and functionalization ofvarious important scaffolds.

Indium chloride is cheap, nontoxic, stable to water andmoisture and easy to handle, all these protocol represents anoptimal development with regard to economic and ecologicalconsideration.

Major challenge in future would be to explore the utility ofInCl3 catalyzed protocol for the synthesis of hithertoinaccessible and highly complex scaffolds.

REFERENCES

Maya Shankar Singh, Keshav Raghuvanshi

TETRAHEDRON Report number 987.

Department of Chemistry (Centre of advanced Study), Faculty of Science, Banaras Hindu

University, Varanasi 221005, India.

Received on 31 may 2012