Synthesis of amides and amines from aldehydes or ketones by heterogeneous metal catalysis

Method according to the previous claim wherein the aldehyde is of formula

• wherein R is selected from substituted or unsubstituted alkyl, cycloalkyl, aryl, cinnamyl and heterocyclic groups.

Method according to the previous claim wherein the ketone is of formula

• wherein R and R1 are selected from substituted or unsubstituted alkyl, cycloalkyl, aryl and heterocyclic groups.

Method according to any one of the previous claims, wherein the heterogeneous metal catalyst is a heterogeneous palladium (Pd) catalyst, preferably a Pd(0) catalyst, more preferably a Pd(0)-nanoparticle catalyst

Method according to any one of the previous claims, wherein the heterogeneous palladium catalyst is selected from Pd0-AmP-MCF (palladium(0)-aminopropyl-mesocellular foam) and Pd0-AmP-CPG (palladium(0)-aminopropyl-controlled pore glass).

Method according to any one of the previous claim, wherein the step of converting the aldehyde or ketone to an amine is catalyzed by a heterogeneous metal catalyst in the presence of an amine donor and reducing agent.

Method according to the previous claim, wherein the amine donor is selected from:

• ammonium formate (HCO2NH4) or a derivative thereof, and
• amine.

Method according to any one of the previous claims, wherein the step of converting the aldehyde or ketone to an amine is carried out at a temperature of at least 22° C., preferably at 60-100° C., wherein the an organic solution is used as a solvent.

Method according to any one of the previous claims, wherein the step of converting the amine to an amide is carried out in the presence of an acyl donor, wherein said acyl donor is an acylating agent selected from acids, esters, alkyl ketene dimers, acid chlorides and anhydrides.

Method according to any one of the previous claims, wherein the step of converting the amine to an amide is catalyzed by a heterogeneous metal catalyst and/or an enzyme.

Method according to any one of the previous claims, wherein

• the step of converting the aldehyde or ketone to an amine is catalyzed by Pd0-AmP-MCF or Pd0-AmP-CPG,
• the step of converting the amine to an amide is catalyzed by Pd0-AmP-MCF and enzyme in the presence of acyl donor.

Method according to any one of the previous claims, wherein the enzyme is selected from lipase and amine transaminase (ATA), wherein

• the lipase is preferably lipase B, more preferably the lipase is CALB (Candida antarctica lipase B), wherein lipase B is optionally immobilized on a macroporous anionic resin, and wherein
• the amine transaminase is preferably selected from ATA-117, ATA-113 and CV-ATA (Chromobacterium violacum ATA), more preferably (R)-selective ATA or (S)-selective ATA.

Method according to any one of the previous claims, wherein

• the step of converting the aldehyde or ketone to an amine is catalyzed by Pd0-AmP-MCF or Pd0-AmP-CPG, and wherein methanol or toluene is used as solvent,
• the step of converting the amine to an amide is catalyzed by Pd0-AmP-MCF and enzyme in the presence of acyl donor, wherein the enzyme is preferably selected from lipase and ATA, and wherein
• toluene is used as solvent.

Method according to any one of the previous claims, wherein

• the step of converting the aldehyde or ketone to an amine is catalyzed by Pd0-AmP-MCF or Pd0-AmP-CPG, and wherein toluene is used as solvent,
• the step of converting the amine to an amide is catalyzed by Pd0-AmP-MCF and lipase B in the presence of acyl donor, and wherein
• toluene is used as solvent.

Method according to any one of the previous 1-15 and 22-27, wherein the acyl donor is ethyl methoxyacetate.

Method according to the previous claim, wherein the substituents R are identical and wherein R is either H or methoxy.

Method according to any one of the previous claims, wherein said conversion is a one-pot synthesis, preferably, said conversion is performed in one pot without any purification of intermediates.

Method according to any one of the previous claims, wherein the aldehyde or ketone is provided by reacting an alcohol with Pd0-AmP-CPG in the presence of O2, wherein said alcohol is selected from a primary alcohol, secondary alcohol and aldol, preferably said alcohol is vanillyl alcohol, more preferably said alcohol is vanillyl alcohol derived from lignin.

Method for conversion of an aldehyde or ketone comprising the steps of:

• Providing an aldehyde or a ketone,
• Converting the aldehyde or ketone to an amine,
• wherein the conversion to amine is catalyzed by a heterogeneous metal catalyst.

Method according to the previous claim wherein the aldehyde is of formula

• wherein R is selected from substituted or unsubstituted alkyl, cycloalkyl, aryl, cinnamyl and heterocyclic groups.

Method according to any one of the previous claims, wherein the aldehyde or ketone is provided by reacting an alcohol with Pd0-AmP-CPG in the presence of O2, wherein said alcohol is selected from a primary alcohol, secondary alcohol and aldol, wherein said alcohol is selected from a primary alcohol, secondary alcohol and aldol, preferably said alcohol is vanillyl alcohol, more preferably said alcohol is vanillyl alcohol derived from lignin.