Palladium-Catalyzed Intermolecular Aminocarbonylation of Alkenes: Efficient Access of β-Amino Acid Derivatives

Abstract

A novel palladium-catalyzed intermolecular aminocarbonylation of alkenes has been developed in which the employment of hypervalent iodine reagent can accelerate the intermolecular aminopalladation, which thus provides the successful catalytic transformation. The current transformation presents one of the most convenient methods to generate β-amino acid derivatives from simple alkenes.

Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

“…3)3132333435363738394041424344454647484950515253545556575859606162636465666768. Coordination of the nitrogen atom in MeCN 2a with AgCO 3 gives the intermediate A , which sequentially reacts with AgCO 3 to afford the AgCH 2 CN intermediate B and AgHCO 3 .…”

“…( a ) Previous work for 1,2-carboamination of alkenes33343536. ( b ) Our radical-mediated three-component, oxidative carboamination between alkenes, alkyl nitriles and amines using a C–H oxidative functionalization.…”

“…One of the major synthetic targets for such transformations, including diamination789101112131415, aminooxygenation161718192021222324, aminohalogenation252627282930 and carboamination313233343536, is the incorporation of a nitrogen atom (amino, amide or azide groups) across the C–C double bonds to build useful N -containing molecules through the formation of a C–N bond. Despite significant progress in the field, approaches of the alkene carboamination for producing linear N -containing molecules are scarce and remain a great challenge (Fig.…”

“…Despite significant progress in the field, approaches of the alkene carboamination for producing linear N -containing molecules are scarce and remain a great challenge (Fig. 1a): available intermolecular transformations for producing linear N -containing molecules are restricted to the special amination reagents33343536. Further, to our knowledge, three-component carboamination reactions of the alkenes via C–H functionalization have never been reported.…”

A Cooperative Strategy for the Highly Selective Intermolecular Oxycarbonylation Reaction of Alkenes using a Palladium Catalyst

“…[3,4] However, in contrast to the highly efficient intramolecular versions,the intermolecular counterparts of these DFAs are often not as effective.F urthermore, as aresult of their sterically hindered nature,internal alkenes are difficult to activate by palladium catalysts and, consequently,they are much less reactive and/or undergo undesired alkene isomerization reactions. [6] Thus,s tudies aimed at uncovering new methods to promote intermolecular DFAs have as ynthetic significance. However,i nternal alkenes are completely inert under the reaction conditions employed for reactions of their terminal counterparts.…”