Carboxylation catalysts
AssigneeUniversity Court of the University of St Andrews
InventorsSteven P. Nolan, Catherine Cazin
Life of this patent
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Abstract
The use of a complex of the form Z—M—OR in the carboxylation of a substrate is described. The group Z is a two-electron donor ligand, M is a metal and OR is selected from the group consisting of OH, alkoxy and aryloxy. The substrate may be carboxylated at a C—H or N—H bond. The metal M may be copper, silver or gold. The two-electron donor ligand may be a phosphine, a carbene or a phosphite ligand. Also described are methods of manufacture of the complexes and methods for preparing isotopically labelled caboxylic acids and carboxylic acid derivatives.
Claims16
A method of carboxylation, the method comprising:
- contacting a complex of the form Z-M-OR, wherein the group Z is a nitrogen containing heterocyclic carbine, where
- M is copper, silver or gold, and —OR is selected from the group consisting of OH, alkoxy and aryloxy;
- wherein the nitrogen containing heterocyclic carbene ligand is of the form:
- wherein each of the groups R, R1 R2, R3 and R4 are the same or different, and the dashed line in the ring represents optional unsaturation with R1 and R2 absent;
- wherein each R and R1, R2, R3 and R4 are, independently for each occurrence, selected from:
- H, a primary or secondary alkyl group;
- unsaturated alkyl, alkyl-substituted, or unsubstituted phenyl;
- alkyl-substituted or unsubstituted naphthyl;
- alky-substituted or unsubstituted anthracenyl;
- or alkyl-substituted or unsubstituted heterocyclic aromatic rings;
- or
- wherein the nitrogen containing heterocyclic carbene ligand is from one of the formulas I, II, III, or IV:
- wherein each group R5, R6 and R7, is independently for each occurrence selected from:
- H;
- a primary or secondary alkyl group;
- alkyl-substituted or unsubstituted phenyl;
- alkyl-substituted or unsubstituted naphthyl;
- or alkyl-substituted or unsubstituted anthracenyl;
- wherein R8, R9, R10 and R11 are each independently for each occurrence H;
- a primary or secondary alkyl group;
- alkyl-substituted or unsubstituted aryl;
- or in formulas (II) and (IV) together with the carbons carrying them form a fused 4-8 membered carbocylic ring or a fused aromatic ring;
- and
- wherein R12 is alkyl or a cycloalkyl;
- with
- a reactant comprising an alkyl-substituted, halo-substituted, or unsubstituted aromatic compound;
- an alkyl-substituted, halo-substituted, or unsubstituted heteroaromatic compound;
- or an alkyl-substituted, halo-substituted, or unsubstituted heterocyclic compound;
- the reactant comprising a C—H or a N—H bond capable of carboxylation;
- and
- a source of CO2.
A method of carboxylation, the method comprising;
- contacting a complex of the form Z-M-OR, wherein the group Z is a nitrogen containing heterocyclic carbine;
- where
- M is copper, silver or gold, and —OR is selected from the group consisting of OH, alkoxy and aryloxy;
- wherein the nitrogen containing heterocyclic carbene ligand is of the form:
- wherein each of the groups R and R1, are the same or different, and the dashed line in the ring represents optional unsaturation with R1 absent;
- wherein each R and R1 are, independently for each occurrence, selected from:
- H, a primary or secondary alkyl group;
- alkyl-substituted, or unsubstituted phenyl;
- alkyl-substituted or unsubstituted naphthyl;
- alky-substituted or unsubstituted anthracenyl;
- or alkyl-substituted or unsubstituted heterocyclic aromatic rings;
- with
- a reactant comprising an alkyl-substituted, halo-substituted, or unsubstituted aromatic compound;
- an alkyl-substituted, halo-substituted, or unsubstituted heteroaromatic compound;
- or an alkyl-substituted, halo-substituted, or unsubstituted heterocyclic compound;
- the reactant comprising a C—H or a N—H bond capable of carboxylation;
- and
- a source of CO2.
Dependencies are inferred from the claim text.