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8/13/2019 Catalytic Amine Synthesis
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Catalytic Amine Synthesisfrente a distintas bases de Lewis
University of British Columbia
Othoniel Reyes CamachoProfessor: Laurel Schafer
using metal of low cost and low toxicity
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1 Introduction
Amines: Valuable and important class of compounds used in pharmaceutical ,agricultural and industrial areas
Hydroamination
Direct addition of an amine across a carbon-carbon multiple bond
Ricci, A., Modern Amination Methods . Wiley VCH, Weinheim, 2000
Anti-Markovnikov Markovnikov
Most efficient route:amines, imines , enamines
No byproduct – 100% atom economy
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2 Alkynes Hydroamination
General Aspects:
Frauke Pohlki and Sven Doye, The catalytic hydroamination of alkynes.Chem. Soc. Rev. , 2003
Enamine Imine
• Hydroamination of alkynes are “less” difficult than alkenesone
• Hydroamination of alkynes can be seen as an advantagebecause it offers high synthetic flexibility
• Thermodynamically favourable
• Entropically disfavourable
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3 Alkynes Hydroamination Cycle
Doye, S., et al., Angew. Chem. Int. Ed. Engl. 1999, 3389
Amine Activation - deprotonation
[2+2] Cycloadition
RNH 2 Coordination
Proton transfer
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4 Summer Work Diagram
*Internalalkynes: 5% or10% LC , 110 ° C
*
*Internalalkynes: 5% or10% LC , 110 ° C
Not explored with internal alkynes
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5 Alternative Reduction Methods
• The requirements for practical asymmetric synthesis include highstereoselectivity , high rate and productivity, atom economy , costefficiency, operational simplicity, environmental friendliness, andlow-energy consumption.
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6 Hydroamination with a LC Standar Solution and NaBH 4
Reduction
*Internal alkynes: 10%LC , 110 ° C
Alkyne Amine Yield Alkyne Amine Yield
65% 39.11%
77% 90%
112%(Wet)
67.47%
5.72% 6.09%
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7 Hydroamination with a LC Standar Solution and NaBH 4
Reduction
*Internalalkynes: 5% or10% LC , 110 ° C
Alkyne Amine Yield
52%
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8 Hydroamination with a LC StandarSolution and H 2, Pd/C Reduction
*Internalalkynes: 5% or10% LC , 110 ° C
Alkyne Amine Yield
85.28%
80.28%
44.90%
• Atom Economy (atom efficiency)
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9 Results
1H RMR Espectrum
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10 Results
GC-MS Espectrocopy
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11Hydroamination with a LC Standar Solution and Reduction by
Transfer Hydrogenation
Alkyne Amine Yield
Pending
Pending
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12 Results: Transfer Hydrogenation with RuCl2(PPh 3)3
GC-MS Espectrocopy
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13 Acknowledgments
National Autonomous University of Mexico
Faculty of Chemistry UNAM
Institut of Chemistry UNAM
University of British Columbia
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14 Sponsor
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15 Alkynes Hydroamination Cycle (Extended)
Berns F Straub and Rober G Bergman The mechanism of Hydroamination Angw Chem Int Ed 2001
Amine Activation - deprotonation
[2+2] Cycloadition
RNH 2 Coordination
Proton transfer
