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
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