Green Chemistry by Nano-Catalysis

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 Green Chemistry
 

             A new kind of chemical revolution “Green Chemistry” is brewing, 150 years after the first chemical revolution transformed modern life with a host of conveniences. Green chemistry protects the environment, not by cleaning it up, but by inventing new chemistry and new chemical processes that do not pollute. The fundamental idea of green chemistry  is that the manufacturer of a chemical needs to consider what   will happen to human life   after the chemical is generated and introduced into their society.By rethinking chemical design from the ground up, green chemists are developing new ways to manufacture products that fuel the economy and lifestyles, without the damages to the environment that have become all too evident in recent years.
          
 

 

The demands for green and sustainable synthetic methods in the fields of healthcare and fine chemicals, combined with the pressure to produce these substances expeditiously and in an environmentally benign fashion, pose significant challenges to the synthetic chemical community. This objective can be achieved through the development of aqueous synthetic protocols using MW-heating. It should also be noted that the rapid development of “Green Organic Chemistry” is due to the recognition that environmentally friendly products and processes will be economical in the long term as they circumvent the need for treating ‘end-of-the-pipe’ pollutants and byproducts generated by conventional synthesis.

 

 

Nano-Catalysis

 

 Nano-catalysis can be considered as a bridge between homogeneous and heterogeneous catalysis. Because of nano-size, i.e. high surface area, the contact between reactants and catalyst increases dramatically and they can operate in the same manner as homogeneous catalysts (close to homogeneous catalysis), at the same time, due to their insolubility in the reaction solvent, they can be separated out easily from the reaction mixture. Thus, Nano-materials can combine the advantage of both the system, and can offer unique activity with high selectivity.

 

 

 

 

List of  Publications:

 

Reviews

 

1.     Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis.

     Vivek Polshettiwar and R. S. Varma, Chem. Commun.  2009, invited feature article.

 

2.      MW-assisted chemistry: a rapid and sustainable route for synthesis of organics and nanomaterials. Vivek Polshettiwar, M. N. Nadaguada and R. S. Varma, Aus. J. Chem. 2009, 62, 16.

 

3.     Silica-supported palladium catalysts for cross-coupling reactions: syntheses and catalytic applications. Vivek Polshettiwar, Christophe Len and Aziz Fihri, Coord. Chem. Rev. 2009, in press.

 

4.     Aqueous microwave chemistry: a clean and green synthetic tool for rapid drug discovery. Vivek Polshettiwar and R. S. Varma, Chem. Soc. Rev. 2008, 37, 1546.

 

5.     Microwave-assisted organic synthesis and transformations using benign reaction media.Vivek Polshettiwar and R. S. Varma, Acc. Chem. Res. 2008, 41, 629-639.

 

6.     Greener and expeditious synthesis of bio-active heterocycles using microwave irradiation. Vivek Polshettiwar and R. S. Varma, Pure App. Chem. 2008, 80, 777-790.

 

7.     Greener and sustainable pharmaceutical active heterocyclic synthesis.

     Vivek Polshettiwar and R. S. Varma, Curr. Opin. Drug Disc. Devel. 2007, 10, 723-737.

 

8.      Silica supported Pd-catalyst for Heck coupling reaction.

     Vivek Polshettiwar, Arpad Molnar, Tetrahedron 2007, 63, 6949.     

 

9.        Recent advances in thionating reagents for synthesis of organosulfur compounds.

Vivek Polshettiwar and M. P. Kaushik, J. Sulfur Chem. 2006, 27, 353.

 

 

 

Book

1.      Microwave-assisted organic synthesis and nano-catalysis in aqueous medium. Ed. Vivek Polshettiwar and R. S. Varma; will be published in July 2010, Royal Society of Chemistry (Green Chemistry Series, Editor Prof. James Clark), Thomas Graham House, Science Park, Cambridge, CB4 0WF, UK

 

Book Chapters

2.     Alternative heating for green synthesis in water (Photo, Ultrasound, and Microwave).

Vivek Polshettiwar and R. S. Varma, Handbook of Green Chemistry, Ed. Paul Anastas & C. –J. Li, 2009,   WILEY-VCH, Boschstrasse 12, D-69469 Weinheim, Germany.

 

3.      Environmentally benign chemical synthesis via mechanochemical mixing and microwave irradiation.Vivek Polshettiwar and R. S. Varma, Eco-Friendly Processes and Procedures for the Synthesis of Fine Chemicals, Ed. Roberto Ballini; 2009, Royal Society of Chemistry, Thomas Graham House, Science Park, Cambridge, CB4 0WF, UK




Research Articles


 1.      Nanoparticle-supported and magnetically recoverable ruthenium hydroxide catalyst: Efficient      hydration of nitriles to amides in aqueous medium. Vivek Polshettiwar and R. S. Varma, Chem. Eur. J.  2009, 15, 1582-1586.

 

 

2.      Magnetic nanoparticle-supported glutathione:  a conceptually sustainable organocatalyst.

       Vivek Polshettiwar, Babita Baruwati, and R. S. Varma, Chem.Commun.  2009, 1837-1839.  

 

 

 

3.      Catalyst-free transfer hydrogenation: a truly sustainable protocol for reduction of aldehydes and ketones. Vivek Polshettiwar and R. S. Varma, Chem. Sus. Chem.  2009, submitted. 

 

 

4.       Self-assembly of metal oxides into 3D nano-structures: Synthesis and nano-catalysis. Vivek Polshettiwar, Babita Baruwati, and R. S. Varma, ACS Nano  2009, 3, 728-736. 

 

 

 

5.       Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: A selective and sustainable oxidation protocol with high turnover number. Vivek Polshettiwar and R. S. Varma, Org. Biomol. Chem. 2009, 7, 37-40.

 

 

6.       Nanoparticle-supported and magnetically recoverable Nickel catalyst: A robust and economic  hydrogenation and transfer hydrogenation protocol. Vivek Polshettiwar, B. Baruwati, & R. S. Varma, Green Chem. 2009, 11, 127-131.

 

 

 

7.       Glutathione promoted expeditious green synthesis of silver nanoparticles using microwaves. Babita Baruwati, Vivek Polshettiwar and R. S. Varma, Green Chem. 2009, in press.

 

8.       Self-assembly of palladium (Pd) nanoparticles: Synthesis of Pd nanobelts, nanoplates and nanotrees using vitamin B1 and their application in carbon-carbon coupling reactions. M. N. Nadaguada,  Vivek Polshettiwar, and R. S. Varma, J. Mat. Chem. 2009, 19, 2026–2031.

 

9.        Ruthenium hydroxide supported on magnetic nanoparticles: a benign aqueous protocol for hydration of nitriles. Vivek Polshettiwar and R. S. Varma, NATURE Protocol 2009, DOI: 10.1038/nprot.2009.103

 

 

10.     Synthesis of single-crystal micro-pine structured nano-ferrites and their application in catalysis. Vivek Polshettiwar and R. S. Varma, Chem. Commun. 2008, 6318-6320.

 

 

11.     Olefin ring closing metathesis and hydrosilylation reaction in aqueous medium by Grubbs second generation ruthenium catalyst. Vivek Polshettiwar and R. S. Varma, J. Org. Chem. 2008, 73, 7417-7419.

 

12.    Magnetically recoverable supported ruthenium catalyst for hydrogenation of alkynes and transfer   hydrogenation of carbonyl compounds. Babita Baruwati, Vivek Polshettiwar and R. S. Varma, Tetrahedron Lett. 2009, 50, 1215-1218. 

                                                                                                                                        

 13.    Ring-fused aminals: Catalyst and solvent-free microwave-assisted a-amination of nitrogen heterocycles.

        Vivek Polshettiwar and R. S. Varma, Tetrahedron Lett. 2008, 49, 7165-7167.

   

14. Greener and rapid access to amides: Nafion catalyzed Ritter reaction under solvent-free

    condition.

    Vivek Polshettiwar and R. S. Varma,
    Tetrahedron Lett. 2008, 49, 2661.

 


 

15. Novel NHC-Pd organic silica-Synthesis and application in carbon-carbon coupling reaction.
    Vivek Polshettiwar and R. S. Varma,
    Tetrahedron 2008, 64, 4637.

 

     Synthesis of NHC-Pd Organic Silica:

 

    

 Application in C-C Coupling Reaction:

 

 

 


 


16. A greener and expeditious synthesis of pyrazole and diazepine in aqueous medium.

     Vivek Polshettiwar and R. S. Varma,
     Tetrahedron Lett. 2008, 49, 397.

 

 


17.  Polystyrene sulfonic acid catalyzed heterocyclization in aqueous medium: A greener

      approach for synthesis of oxadiazole, and thiadiazole
      Vivek Polshettiwar and R. S. Varma,
      Tetrahedron Lett. 2008, 49, 879.

 

 

 


 

18.  Tandem Bis-Aldol Reaction of Ketones: A Facile One Pot Synthesis of 1,3-Dioxanes in  

      Aqueous Medium.
      Vivek Polshettiwar and R. S. Varma,
      J. Org. Chem. 2007, 72, 7420.

 

 

 


 

19.  Polystyrene sulfonic acid catalyzed greener synthesis of hydrazones in aqueous medium 

       using microwaves.
       Vivek Polshettiwar and R. S. Varma,
       Tetrahedron Lett. 2007, 48, 5649.

 

 

 


20. Biginelli reaction in aqueous medium: A greener and sustainable approach to substituted

     3,4-dihydropyrimidin-2(1H)-ones.
    
Vivek Polshettiwar and R. S. Varma,
     Tetrahedron Lett. 2007, 48, 7343.

 

 


 

21.  An efficient and chemoselective Cbz-protection of amines using silica-sulfuric acid at

      room temperature.
      Manoj, B. Gawande, Vivek Polshettiwar, R. S. Varma and Radha V. Jayaram

      Tetrahedron Lett. 2007, 48, 8170.

 

 

 

 


22. Tandem bis-aza-Micheal reaction of diamines in aqueous medium.

      Vivek Polshettiwar and R. S. Varma,
      Tetrahedron Lett. 2007, 48, 8735.

 

 

 

23.  Expeditious oxidation of alcohols to carbonyl compounds using iron(III) nitrate.
       V. V. Namboodiri, Vivek Polshettiwar and R. S. Varma,
       Tetrahedron Lett. 2007, 48, 8839.

 

 


24.  Palladium containing nano-structured silica functionalized with pyridine sites: a versatile

       heterogeneous catalyst for Heck, Sonogashira and cyanation reactions.
       Vivek Polshettiwar, Peter Hesemann, Joel J. E. Moreau
       Tetrahedron 2007, 63, 6784.


 

 

 

 

 

 

 

25.  Silica hybrid material containing Pd-NHC complex as heterogeneous catalyst for 

       Mizoroki-Heck reactions.
       Vivek Polshettiwar, Peter Hesemann, Joel J. E. Moreau
       Tetrahedron Lett. 2007, 48, 5363.



26.  Highly ordered functional organosilica by template directed hydrolysispolycondensation

       using chiral camphorsulfonamide precursors: Synthesis and application of new task   

       specific ionic liquid.
       Benoit Gadenne, Peter Hesemann, Vivek Polshettiwar and Joel Moreau,
       Eur. J. Inorg. Chem. 2006, 3697.



27.  Alumina encapsulated phosphorus pentasulfide (P4S10/Al2O3) mediated efficient

      thionation of long chain amides.
      Vivek Polshettiwar, and M. P. Kaushik
      Tetrahedron Lett. 2006, 47, 2315.


 

 


28.  Pd(OAc)2/Silica in Ionic Liquid-A Green Heck Catalyst.
      Vivek Polshettiwar
      Res. J. Chem. Environ. 2006, 10, 91.

 

 

29.  N-Octyl quinolinium tribromide: a quinoline based ionic liquid as a new brominating

      agent for bromination of phenols, aromatic amines, alkenes and alkynes.
      Vivek Polshettiwar and M. P. Kaushik
      Ind. J. Chem. B 2006, 45, 2542.

 

 

 

30.  Microwave enhanced chemistry of CsF-Celite: an efficient catalyst for the synthesis of

      esters, ethers and their thio-analogues.
       Vivek Polshettiwar and M. P. Kaushik
       Catalysis Commun. 2005, 6,191.

 

 

31.  Tighter ion pair effect and Scale-Up study in microwaves assisted aminolysis of

       enolizable esters using potassium tert-butoxide (t-BuOK).
       Vivek Polshettiwar and M. P. Kaushik
       Ind. J. Chem. B 2005, 44, 773.


32.   A new, efficient and simple method for the thionation of ketones to thioketones using

       P4S10/Al2O3.
       Vivek Polshettiwar and M. P. Kaushik
       Tetrahedron Lett. 2004, 45, 6255.

 



33.  CsF-Celite catalyzed regio- and chemoselective SN2 type ring opening of epoxides with

       thiol.
       Vivek Polshettiwar and M. P. Kaushik
       Catalysis Commun. 2004, 5, 515.

 

 



34.   Phosphorus Pentasulfide (P4S10)
       Vivek Polshettiwar
       Synlett. 2004, 2245.


35.  Thionation of carbonyl compounds by phosphorus pentasulfide and

       hexamethyldisiloxane under microwave irradiations.
       Vivek Polshettiwar, Manisha Nivsarkar, Deepak Pardashani and M. P. Kaushik
       J. Chem. Res. 2004, 474.


36.   A new reagent for the efficient synthesis of disulfides from alkyl halides.
       Vivek Polshettiwar, Manisha Nivsarkar, Jyotiranjan Acharya and M. P. Kaushik
       Tetrahedron Lett. 2003, 44, 887.

 

 

37.   Synthesis of new chiral ionic liquid

       Vivek Polshettiwar
       unpublished work