Palladium catalyzed
intermolecular
aminocarbonylation of
alkenes
J. Cheng, X. Qi, M. Li, P. Chen,
G. Liu, JACS, 2015, 137, 2480.
RCC Mylène ROUDIER
19,03,2015
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b-amino acids
 b-aminoacids identified as essential component in natural products
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b-amino acids
 b-aminoacids identified as essential component in natural products
3
b-amino acids synthesis
 Amination of a,b-insaturated carboxylic acids
Chem. Soc. Rev., 1996, 117-128
For a recent review of asymmetric synthesis of a- and b-amino acids : ACIE, 2003, 42, 4290-4299.
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b-amino acids synthesis
 Amination of a,b-insaturated carboxylic acids
 Amination of a,b-insaturated esters
Chem. Soc. Rev., 1996, 117-128
For a recent review of asymmetric synthesis of a- and b-amino acids : ACIE, 2003, 42, 4290-4299.
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b-amino acids synthesis
 Hydrogenation of b- aminoacrylic acids
Chem. Soc. Rev., 1996, 117-128
For a recent review of asymmetric synthesis of a- and b-amino acids : ACIE, 2003, 42, 4290-4299.
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 Direct amination of olefins
This work
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 Direct amination of olefins
This work
5
This work
 Direct amination of olefins
-> Pd-benzoquinone or Pd-Cu(II) salt systems as oxidants for aminocarbonylation
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This work
 Direct amination of olefins
-> Pd-benzoquinone or Pd-Cu(II) salt systems as oxidants for aminocarbonylation
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 Direct amination of olefins
X k2 > k1
How to favor the aminopalladation ?
This work
5
 Direct amination of olefins
X k2 > k1
How to favor the aminopalladation ?
This work
5
 Direct amination of olefins
X k2 > k1
How to favor the aminopalladation ?
This work
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This work
 Direct amination of olefins
80%
X k2 > k1
How to favor the aminopalladation ?
 k2 << k1
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Optimization
Due to oxycarbonylation
reaction
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Optimization
Due to oxycarbonylation
reaction
Best conditions
6
Optimization
Due to oxycarbonylation
reaction
Best conditions
Strong oxidants
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Optimization
Due to oxycarbonylation
reaction
Best conditions
Without palladium
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Role of PhI(O2CAd)2
Some examples..
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Reaction scope
Unreactive alkenes..
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Reaction scope
Deuterium labeling..
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Stereochemistry
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Mechanism
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Conclusion
• First intermolecular aminocarbonylation pallado-catalyzed.
• Functionnalized b-aminoacids from simple and available alkenes.
• PhI(O2CAd)2 not only used as oxidant but can improve the
reactivity of Pd catalyst.
• The mechanism need to be more studied to understand exactly
the role of the hypervalent iodine.
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Conclusion
 Thank you for your attention