Nano-to-nano Fe/ppm Pd catalysis of cross-coupling reactions in water

Patent metadata

Field	Value
Publication number	US-9956551-B2
Application number	US-201615158238-A
Country	US
Kind code	B2
Filing date	May 18, 2016
Priority date	May 19, 2015
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

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.

First claim

What is claimed is:

1. 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 using a reducing agent, 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.

2. The composition of claim 1 , wherein the iron is selected from the group consisting of a Fe(II) or Fe(III) salt, a Fe(II) salt precursor or Fe(III) salt precursor.

3. The composition of claim 1 , wherein the palladium is naturally present in the iron salt in amounts less than or equal to 1 ppm, 10 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm or 500 ppm relative to the iron salt or iron complex.

4. The composition of claim 3 , where the amount of Pd present is controlled by external addition of a Pd salt to an iron salt.

5. The composition of claim 1 , wherein the reducing reagent is a Grignard reagent selected from the group consisting of MeMgCl, MeMgBr, MeMgI, EtMgCl, EtMgBr, EtMgI, i-PrMgCl, i-PrMgBr, i-PrMgI, PhMgCl, PhMgBr, PhMgI, n-hexyl-MgBr, n-hexyl-MgCl, n-hexyl-MgBr, n-hexyl-MgCl, n-hexyl-MgI, NaBH 4 , liBH 4 , BH 3 -THF, BH 3 —SMe 2 , borane, DIBAL-H and LiAlH 4 ; and mixtures thereof.

6. The composition of claim 1 , wherein the surfactant is selected from the group consisting of TPGS-500, TPGS-500-M, TPGS-750, TPGS-750-M, TPGS-1000 and TPGS-1000-M, Nok and PTS, or a mixture thereof.

7. The composition of claim 1 , further comprising a ligand selected from the group consisting of PPh 3 , (o-Tol) 3 P, (p-Tol) 3 P, dppf, dtbpf, BiDime, Tangphos, IMes, IPr, SPhos, t-BuSPhos, XPhos, t-BuXPhos, BrettPhos and t-BuBrettPhos, and HandaPhos or an analog thereof.

8. The composition of claim 1 , wherein the iron metal complex as nanoparticles is heterogeneous and can be isolated from the composition, stored and recycled.

9. The composition of claim 1 , wherein the reaction solvent is water, and the reaction solvent further comprising an organic solvent, wherein the organic co-solvent is present in at least 5%, 10%, 20%, 30%, 40%, 50%, 70%, 80% or at least 90% wt/wt.

Assignees

• Lipshutz Bruce H
• Handa Sachin
• Univ California

Inventors

• Lipshutz Bruce H
• Handa Sachin

Classifications

• C07D317/22

  etherified · CPC title

• C07C271/28

  to a carbon atom of a non-condensed six-membered aromatic ring · CPC title

• C07D409/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C07D401/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• B01J2231/4227

  with Y= Cl · CPC title