In one embodiment, the present application discloses a catalyst composition comprising: a) a reaction solvent or a reaction medium; b) organometallic nanoparticles comprising: i) a nanoparticle (NP) catalyst, prepared by a reduction of an iron salt in an organic solvent, wherein the catalyst comprises at least one other metal selected from the group consisting of Pd, Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or mixtures thereof; c) a ligand; and d) a surfactant; wherein the metal or mixtures thereof is present in less than or equal to 50,000 ppm relative to the iron salt.

Polydentate macrocyclic NHCs (NHC ligands) and related methods are disclosed. Such ligands advantageously facilitate a variety of ligand coordination modes and stabilize oxidation states of metal complexes with a number of coordination environments and shapes. The NHC ligands described herein comprise pendant groups configured to facilitate a variety of reactions including: cis-trans isomerization, proton shuttling and facilitating changes in coordination environments as a result of redox reactions.

In one embodiment, the present application discloses a catalyst composition comprising: a) a reaction solvent or a reaction medium; b) organometallic nanoparticles comprising: i) a nanoparticle (NP) catalyst, prepared by a reduction of an iron salt in an organic solvent, wherein the catalyst comprises at least one other metal selected from the group consisting of Pd, Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or mixtures thereof; c) a ligand; and d) a surfactant; wherein the metal or mixtures thereof is present in less than or equal to 50,000 ppm relative to the iron salt.

The present invention provides a complex of formula (1),

##STR00001##

wherein, M is palladium or nickel, R.sub.1 and R.sub.2 are independently organic groups having 1-20 carbon atoms, or R.sub.1 and R.sub.2 are linked to form a ring structure with the phosphorus atom, R.sub.3 is selected from the group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, and substituted and unsubstituted metallocenyl, R.sub.4 is an organic group having 1-20 carbon atoms, n is 0, 1, 2, 3, 4 or 5, and X is an anionic ligand. The invention also provides a process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions.

A complex of formula (1), ##STR00001##
wherein, M is palladium or nickel, R.sub.1 and R.sub.2 are independently organic groups having 1-20 carbon atoms, or R.sub.1 and R.sub.2 are linked to form a ring structure with the phosphorus atom, R.sub.3 is selected from the group consisting of substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, and substituted and unsubstituted metallocenyl, R.sub.4 is an organic group having 1-20 carbon atoms, n is 0, 1, 2, 3, 4 or 5, X is an anionic ligand. A process for the preparation of the complex, and its use in carbon-carbon or carbon-nitrogen coupling reactions is also provided.

A process for producing an aromatic compound in high yield and a palladium complex are provided. The palladium complex is represented by formula (D) or formula (D):

##STR00001##

In formula (D), X represents a chlorine atom, A represents an alkyl group having 1 to 3 carbon atoms, B represents an alkyl group having 4 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, R.sup.4 and R.sup.5 each independently represent a hydrogen atom, a fluorine atom, or an alkoxy group having 1 to 20 carbon atoms, and R.sup.6, R.sup.7 and R.sup.8 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms.

##STR00002##

In formula (D), X, A, B and R.sup.4 to R.sup.8 are the same as defined above.

A solid-supported Pd catalyst is suitable for CC bond formation, e.g., via Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions, with a support that is reusable, cost-efficient, regioselective, and naturally available. Such catalysts may contain Pd nanoparticles on jute plant sticks (GS), i.e., Pd@GS, and may be formed by reducing, e.g., K.sub.2PdCl.sub.4 with NaBH.sub.4 in water, and then used this as a dip catalyst. The dip catalyst can catalyze Suzuki-Miyaura and Mizoroki-Heck cross coupling-reactions in water. The catalysts may have a homogeneous distribution of Pd nanoparticles with average dimensions, e.g., within a range of 7 to 10 nm on the solid support. Suzuki-Miyaura cross-coupling reactions may achieve conversions of, e.g., 97% with TOFs around 4692 h.sup.?1, Mizoroki-Heck reactions with conversions of, e.g., a 98% and TOFs of 237 h.sup.?1, while the same catalyst sample may be used for 7 consecutive cycles, i.e., without addition of any fresh catalyst.

A solid-supported Pd catalyst is suitable for CC bond formation, e.g., via Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions, with a support that is reusable, cost-efficient, regioselective, and naturally available. Such catalysts may contain Pd nanoparticles on jute plant sticks (GS), i.e., Pd@GS, and may be formed by reducing, e.g., K.sub.2PdCl.sub.4 with NaBH.sub.4 in water, and then used this as a dip catalyst. The dip catalyst can catalyze Suzuki-Miyaura and Mizoroki-Heck cross coupling-reactions in water. The catalysts may have a homogeneous distribution of Pd nanoparticles with average dimensions, e.g., within a range of 7 to 10 nm on the solid support. Suzuki-Miyaura cross-coupling reactions may achieve conversions of, e.g., 97% with TOFs around 4692 h.sup.?1, Mizoroki-Heck reactions with conversions of, e.g., a 98% and TOFs of 237 h.sup.?1, while the same catalyst sample may be used for 7 consecutive cycles, i.e., without addition of any fresh catalyst.

A solid-supported Pd catalyst is suitable for CC bond formation, e.g., via Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions, with a support that is reusable, cost-efficient, regioselective, and naturally available. Such catalysts may contain Pd nanoparticles on jute plant sticks (GS), i.e., Pd@GS, and may be formed by reducing, e.g., K.sub.2PdCl.sub.4 with NaBH.sub.4 in water, and then used this as a dip catalyst. The dip catalyst can catalyze Suzuki-Miyaura and Mizoroki-Heck cross coupling-reactions in water. The catalysts may have a homogeneous distribution of Pd nanoparticles with average dimensions, e.g., within a range of 7 to 10 nm on the solid support. Suzuki-Miyaura cross-coupling reactions may achieve conversions of, e.g., 97% with TOFs around 4692 h.sup.?1, Mizoroki-Heck reactions with conversions of, e.g., a 98% and TOFs of 237 h.sup.?1, while the same catalyst sample may be used for 7 consecutive cycles, i.e., without addition of any fresh catalyst.

Improved methods of synthesizing 6-aryl-4-aminopicolinates, such as arylalkyl and alkyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates and arylalkyl and alkyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylates, are described herein. The improved methods include a direct Suzuki coupling step, which eliminates the protection/de-protection steps in the current chemical process, and therefore eliminates or reduces various raw materials, equipment and cycle time as well as modification of other process conditions including use of crude AP, use of ABA-diMe, and varying pH, catalyst concentration, solvent composition, and/or workup procedures. This includes synthesis of 2-aryl-6-aminopyrimidine-4-carboxylates.