this ppt represents recently published organic letters for the tandem synthesis of aminoquinolines derivatives via povarov reaction and hydrogen transfer

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Pilani Campus
Povarov-Reductive Amination Cascade to Access
6-Aminoquinolines and Anthrazolines
Kasiviswanadharaju Pericherla, August 30, 2013

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 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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