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US 12,729,216 B2Granted
Ferrocene-based unsymmetrical ligands bearing bulky di(adamantyl)phosphino motif and their metal catalysts
AssigneeSigma-Aldrich Co.
InventorsGuolin Xu, Thomas Colacot, Peng Gao
Life of this patent
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Abstract
Ferrocenyl-based unsymmetrical ligands containing di(1-adamantyl)phosphino groups with general formula, Fc(Ad2P) (R2P) and corresponding metal complexes, include metal halide complexes, N-biphenyl metal cationic complexes and R-allyl metal cationic complexes, useful in catalysis. The ligands and complexes overcome problems with conventional catalysts, providing new routes to previously challenging cross-coupling reactions, including C—P coupling, Csp2-Csp3 coupling and other conventional cross-coupling applications, while being scalable so that they can be provided in sufficient quantity and purity for industrial applications.
Claims36
A compound of formula I
- wherein
- R1 and R2 are independently selected from the group consisting of C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, —NR4R5, and optionally substituted phenyl;
- R4 and R5 are individually selected from the group consisting of H and C1-C12 alkyl, or R4 and R5 together can form a saturated or unsaturated 5- or 6-membered ring, the ring optionally including one or more additional heteroatoms selected from O, S and N, and one or more optional substituents;
- and
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy.
2 more elements
A ligand of formula I:
- wherein
- R1 and R2 are independently selected from the group consisting of C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, —NR4R5, and optionally substituted phenyl;
- R4 and R5 are individually selected from the group consisting of H and C1-C12 alkyl, or R4 and R5 together can form a saturated or unsaturated 5- or 6-membered ring, the ring optionally including one or more additional heteroatoms selected from O, S and N, and one or more optional substituents;
- and
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy.
2 more elements
A precatalyst of formula II:
- wherein
- Ad is adamantyl;
- R1 and R2 are independently selected from the group consisting of C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, —NR4R5, and optionally substituted phenyl;
- R4 and R5 are individually selected from the group consisting of H and C1-C12 alkyl, or R4 and R5 together can form a saturated or unsaturated 5- or 6-membered ring, the ring optionally including one or more additional heteroatoms selected from O, S and N, and one or more optional substituents;
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy;
- M is a transition metal selected from Group 9 or Group 10;
- and
- Y is halo.
5 more elements
A precatalyst of Formula III:
- wherein
- Ad is adamantyl;
- R1 and R2 are independently selected from the group consisting of C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, —NR4R5, and optionally substituted phenyl;
- R4 and R5 are individually selected from the group consisting of H and C1-C12 alkyl, or R4 and R5 together can form a saturated or unsaturated 5- or 6-membered ring, the ring optionally including one or more additional heteroatoms selected from O, S and N, and one or more optional substituents;
- each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy;
- M is a transition metal selected from Group 9 or Group 10;
- X is selected from the group consisting of H, C1-C4 alkyl and phenyl;
- and
- Y″ is an anion selected from the group consisting of halide, triflate (−OTf), tetrafluoroborate (−BF4), hexafluorophosphate (−PF6), mesylate (−OMs), tosylate (−OTs), tetrakis [3,5-bis(trifluoromethyl)phenyl]borate (−BArF), hexafluoro antimonate (−SbF6) and combinations thereof.
6 more elements
A precatalyst of formula IV:
- wherein
- Ad is adamantyl;
- R1 and R2 are independently selected from the group consisting of C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, —NR4R5, and optionally substituted phenyl;
- R4 and R5 are individually selected from the group consisting of H and C1-C12 alkyl, or R4 and R5 together can form a saturated or unsaturated 5- or 6-membered ring, the ring optionally including one or more additional heteroatoms selected from O, S and N, and one or more optional substituents;
- wherein each optional substituent, when present, is selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy;
- M is a transition metal selected from Group 9 or Group 10;
- X is selected from the group consisting of H, C1-C4 alkyl and phenyl;
- and
- Y− is an anion selected from the group consisting of halide, triflate (−OTf), tetrafluoroborate (−BF4), hexafluorophosphate (−PF6), mesylate (−OMs), tosylate (−OTs), tetrakis [3,5-bis(trifluoromethyl)phenyl]borate (−BArF), hexafluoro antimonate (−SbF6) and combinations thereof.
6 more elements
Dependencies are inferred from the claim text.