1. No category

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
2
b-amino acids
 b-aminoacids identified as essential component in natural products
3
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.
3
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.
4
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.
5
 Direct amination of olefins
This work
5
 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
5
This work
 Direct amination of olefins
-> Pd-benzoquinone or Pd-Cu(II) salt systems as oxidants for aminocarbonylation
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
5
 Direct amination of olefins
X k2 > k1
How to favor the aminopalladation ?
This work
5
This work
 Direct amination of olefins
80%
X k2 > k1
How to favor the aminopalladation ?
 k2 << k1
6
Optimization
Due to oxycarbonylation
reaction
6
Optimization
Due to oxycarbonylation
reaction
Best conditions
6
Optimization
Due to oxycarbonylation
reaction
Best conditions
Strong oxidants
6
Optimization
Due to oxycarbonylation
reaction
Best conditions
Without palladium
7
Role of PhI(O2CAd)2
Some examples..
8
Reaction scope
Unreactive alkenes..
9
Reaction scope
Deuterium labeling..
10
Stereochemistry
11
Mechanism
12
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.
12
Conclusion
 Thank you for your attention