High-valent palladium fluoride complexes and uses thereof
AssigneePresident and Fellows of Harvard College
InventorsTakeru Furuya, David Powers, Tobias Ritter
Life of this patent
Estimating the term…
Abstract
The present invention provides novel high-valent palladium fluoride complexes. The complexes typically include multi-dentate ligands that stabilize the octahedral coordination sphere of the palladium(IV) atom. These complexes are useful in fluorinating organic compounds, in particular aryl-containing compounds. The invention is particularly useful for fluorinating compounds with 19F for PET imaging.
Claims42
A palladium complex of formula (I):
- wherein:
- the dashed line represents the presence or absence of a bond;
- Pd has a valency of +4;
- n is an integer between 0 and 4, inclusive;
- m is an integer between 0 and 3, inclusive;
- each occurrence of RA is independently hydrogen;
- halogen;
- cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic;
- cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic;
- substituted or unsubstituted, branched or unbranched acyl;
- substituted or unsubstituted, branched or unbranched aryl;
- substituted or unsubstituted, branched or unbranched heteroaryl;
- —OR′;
- —C(═O)R′;
- —CO2R′;
- —CN;
- —SCN;
- —SR′;
- —SOR′;
- —SO2R′;
- —NO2;
- —N(R′)2;
- —NHC(O)R′;
- or —C(R′)3;
- wherein each occurrence of R′ is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety;
- an aryl moiety;
- a heteroaryl moiety;
- alkoxy;
- aryloxy;
- alkylthio;
- arylthio;
- amino, alkylamino, dialkylamino, heteroaryloxy;
- or heteroarylthio moiety;
- wherein two RA may be taken together to form a substituted or unsubstituted carbocyclic, heterocyclic, aryl or heteroaryl ring;
- each occurrence of RB is independently hydrogen;
- halogen;
- cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic;
- cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic;
- substituted or unsubstituted, branched or unbranched acyl;
- substituted or unsubstituted, branched or unbranched aryl;
- substituted or unsubstituted, branched or unbranched heteroaryl;
- —OR″;
- —C(═O)R″;
- —CO2R″;
- —CN;
- —SCN;
- —SR″;
- —SOR″;
- —SO2R″;
- —NO2;
- —N(R″)2;
- —NHC(O)R″;
- or —C(R″)3;
- wherein each occurrence of R″ is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety;
- an aryl moiety;
- a heteroaryl moiety;
- alkoxy;
- aryloxy;
- alkylthio;
- arylthio;
- amino, alkylamino, dialkylamino, heteroaryloxy;
- or heteroarylthio moiety;
- each occurrence of RC is independently hydrogen;
- cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic;
- cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic;
- substituted or unsubstituted, branched or unbranched acyl;
- substituted or unsubstituted, branched or unbranched aryl;
- substituted or unsubstituted, branched or unbranched heteroaryl;
- wherein RC and RB may be taken together to form a substituted or unsubstituted heterocyclic or heteroaryl ring;
- and wherein RC and RA may be taken together to form a substituted or unsubstituted carbocyclic, heterocyclic, aryl or heteroaryl ring;
- RD1, RD2, RD3, and RD4 are each independently cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic;
- cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic;
- substituted or unsubstituted, branched or unbranched aryl;
- substituted or unsubstituted, branched or unbranched heteroaryl;
- Z− is an anion such as halide, acetate, tosylate, azide, tetrafluoroborate, tetraphenylborate, tetrakis(pentafluorophenyl)borate, [B[3,5-(CF3)2C6H3]4]−, hexafluorophosphate, phosphate, sulfate, perchlorate, trifluoromethanesulfonate or hexafluoroantimonate;
- and
- F comprises 18F or 19F.
3-5. (canceled)
10-12. (canceled)
15-19. (canceled)
(canceled)
25-34. (canceled)
A method of fluorinating an organic compound, the method comprising mixing a palladium complex of formula (I) with a substrate under conditions sufficient to fluorinate the substrate, thereby providing a fluorinated organic compound.
45-55. (canceled)
57-58. (canceled)
60-64. (canceled)
66-78. (canceled)
80-150. (canceled)
A method of making a fluorinated Pd(IV) complex, the method comprising reacting a palladium complex of formula (II) with a fluorinating agent, to provide the fluorinated Pd(IV) complex.
153-209. (canceled)
A method of preparing a palladium fluoride complex of formula:
- the method comprising steps of:
- reacting a palladium chloride complex of formula:
- with nucleophilic F− under suitable conditions to yield a complex of formula:
Dependencies are inferred from the claim text.