kasiviswanadharaju pericherla, tandem povarov reaction, hydrogen transfer

BITS Pilani Pilani Campus

Povarov-Reductive Amination Cascade to Access 6-Aminoquinolines and Anthrazolines

Kasiviswanadharaju Pericherla, August 30, 2013

BITS Pilani, Pilani Campus

Introduction Results and Discussion Conclusion Acknowledgements

Contents of the Seminar

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Quinolines derivatives

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Lit. for the synthesis of Anthrazolines

Ref# 1) Eilaf Ahmed , Alejandro L. Briseno , Younan Xia ,and Samson A. Jenekhe, J. Am. Chem. Soc. 2008, 130, 1118.

2) Christopher J. Tonzola , Maksudul M. Alam , Werner Kaminsky , and Samson A. Jenekhe,J. Am. Chem. Soc. 2003,

125, 13548.

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Povarov reaction

Ref# L. S. Povarov, Russian. Chem. Rev, 1967, 36, 656.

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Imine as oxidizing agent

Ref# R. Leardini, D. Nanni, A. Tundo, G. Zanardi, F. Ruggieri, J. Org. Chem, 1992, 57, 1842.

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Imine as oxidizing agent

Ref# N. Shindoh, H. Tokuyama, Y. Takemoto and K. Takasu, J. Org. Chem, 2008, 73, 7451.

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Imine as oxidizing agent

Ref# V. Gaddam, S. Ramesh and R. Nagarajan, Tetrahedron, 2010, 66, 4218.

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Our approach

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Our approach

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Entry Catalyst Solvent Yieldb

1 BF3-Et2O CH3CN 36

2 BF3-Et2O CH3CN 44c

3 AlCl3 CH3CN 22

4 p-TSA CH3CN 18

5 CF3CO2H CH3CN trace

6 CH3CO2H CH3CN NDd

7 Sc(OTf)3 CH3CN 39

8 Cu(OTf)2 CH3CN 22

9 Y(OTf)3 CH3CN 29

10 Yb(OTf)3 CH3CN 48

11 CANe CH3CN 16

12 Cyanuric chloride CH3CN 12

13 Yb(OTf)3 1,4-Dioxane 15

14 Yb(OTf)3 Toluene NDd

15 Yb(OTf)3 DCEf 18

16 Yb(OTf)3 DMFg NDd

17 Yb(OTf)3 DMEh trace aReaction conditions: 1 (1.0 mmol), 2 (2.0 mmol), 3 (1.5 mmol), Catalyst (0.05 mmol), Solvent (3.0 mL), 80 °C, 14 h. bIsolated yields. cCatalyst (20 mol%). dNot

Detected. eCeric ammonium nitrate. f1,2-Dichloroethane. gN,N-Dimethylformamide. h1,2-Dimethoxyethane

Optimization

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Diversifying the methodology

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Diversifying the methodology

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Utility of new compounds

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• A new tandem multicomponent approach has been introduced for the synthesis N-arylmethyl-6-amino-2,4-diarylquinolines via Povarov reaction, dehydrogenation and imine reduction. • An array of 6-aminoquinoline derivatives have been synthesized to demonstrate the scope of the standardized condition. • Removal of the N-benzyl group on a representative molecule by catalytic hydrogenation resulted in 6-amino-2,4-diphenylquinoline, which was utilized in making symmetrical and unsymmetrical anthrazoline derivatives. • This work represents the first report for the synthesis unsymmetrical anthrazolines using 1,4-phenylenediamine.

Conclusion

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